KR20090033103A - Electroluminescence device and method for producing the same - Google Patents

Abstract

An electroluminescent device and a manufacturing method thereof are provided to pattern a light emitting layer by using a difference of a wettability change pattern. A first electrode layer(2) is formed on a substrate(1). A wettability change layer(4) is formed on the substrate, and includes an optical catalyst. A wettability of the wettability change layer is changed by an optical catalyst according to an energy irradiation. The energy is irradiated on the wettability change layer into a patterning mode. A wettability change pattern is formed on a surface of the wettability change layer, and includes a lyophilic region(5) and a liquid-repellent region(6). A coating liquid for forming a light emitting layer including quantum dots is coated on the wettability change layer. A light emitting layer(7) is formed on the lyophilic region.

Description

EL device and its manufacturing method {ELECTROLUMINESCENCE DEVICE AND METHOD FOR PRODUCING THE SAME}

This patent application is based on Japanese Patent Application No. 2007-256852 which is a Japanese application filed on September 28, 2007. The entire disclosure in this application is a part of this specification by citing.

The present invention provides a method for producing an electroluminescent (hereinafter sometimes referred to as EL) element in which patterning of a light emitting layer containing quantum dots is performed using a layer whose wettability is changed by the action of a photocatalyst according to energy irradiation. It relates to an EL device thus obtained.

The EL element combines holes and electrons injected from two opposite electrodes in the light emitting layer, excites the light emitting material in the light emitting layer with the energy, and emits light in accordance with the light emitting material. It is attracting attention.

In general, in the manufacture of a display using an EL element, the light emitting layer is patterned. As the patterning method of the light emitting layer, various patterning methods have been proposed, such as a method of depositing a light emitting material through a shadow mask, a method of split coating by inkjet, a method of destroying a specific light emitting pigment by ultraviolet irradiation, and a screen printing method. Moreover, in the division coating method by inkjet, in order to obtain a high-precision fine pattern, it is proposed to form a patterned partition (bank) and to ink-reduce the partition surface (for example, patent document 1 and a patent document). 2). Moreover, as a method of patterning a light emitting layer, the method of using the photocatalyst which enables high-precision pattern formation is also proposed (for example, refer patent document 3-patent document 6).

The patterning method of the light emitting layer using this photocatalyst is that when the layer containing the photocatalyst or the layer close to the layer containing the photocatalyst is irradiated with energy, the wettability of these layers is changed from the action of the photocatalyst accordingly. It is used. That is, the light emitting layer is formed in a pattern by using a pattern due to this wettability difference. Thus, the patterning method of the light emitting layer using a photocatalyst is a useful method in that the pattern required by the difference in wettability can be formed only by irradiation of energy, and the time required for patterning of the light emitting layer can be largely omitted.

Moreover, the light emitting element which has a light emitting layer using the quantum dot containing a semiconductor is proposed and developed in recent years. A quantum dot is composed of a plurality of atoms of a semiconductor to form a crystal of a few nm to several tens of nm, and when the crystal is reduced to such a nano-size, it constitutes a discrete energy level rather than a continuous band structure. That is, since the quantum size effect is remarkable, the shielding effect of the electrons is higher than that of the bulk crystal larger in size than the quantum dots, and the probability of recombination of the excitons can be increased.

In the light emitting element using the quantum dots, the light emission frequency can be adjusted without changing the configuration of the light emitting element. Quantum dots exhibit optical properties that depend on size by the quantum shielding effect. For example, the emission color of quantum dots containing CdSe can be changed from blue to red by simply changing the size of the quantum dots. In addition, since the quantum dots emit light at a relatively narrow half width, the half width can be, for example, less than 30 nm. Therefore, it can be said that quantum dots are excellent as a material of a light emitting layer.

In addition, although a quantum dot may be called nanocrystal, microparticles | fine-particles, a colloid, or a cluster, etc., what generate | occur | produces a quantum size effect shows the same thing as a quantum dot in this invention.

As a method of forming a light emitting layer using such quantum dots, for example, a spin coating method using a colloidal solution containing a quantum dot having a ligand such as tri-n-octylphosphine oxide (TOPO) attached to the surface, an immersion coating method, or the like This is known (for example, refer patent document 7, patent document 8). This ligand is attached to the surface of the quantum dots to improve the dispersion stability of the quantum dots.

[Patent Document 1] Japanese Patent No. 3601716

[Patent Document 2] Japanese Patent No. 3646510

[Patent Document 3] Japanese Patent Application Laid-Open No. 2001-257073

[Patent Document 4] Japanese Patent Application Laid-Open No. 2002-231446

[Patent Document 5] Japanese Patent Application Laid-Open No. 2004-71286

[Patent Document 6] Japanese Patent Application Laid-Open No. 2005-300926

[Patent Document 7] Japanese Patent Publication No. 2005-522005

[Patent Document 8] Japanese Patent Publication No. 2006-520077

However, little is proposed about the method of patterning the light emitting layer formed into a film using said quantum dot.

This invention is made | formed in view of the said situation, Comprising: It aims at providing the manufacturing method of the EL element which can easily pattern the light emitting layer containing a quantum dot.

MEANS TO SOLVE THE PROBLEM As a result of performing various examination in order to solve the said subject, in order to pattern the light emitting layer using a quantum dot, it is necessary to form a lyophilic pattern on a board | substrate, and to hold a coating liquid in a desired position, and a photocatalyst. And an organopolysiloxane which exhibits liquid repellency, and has been found to be able to achieve patterning of a light emitting layer using quantum dots by applying a wettability changing layer capable of exhibiting a hole transporting function and a photocatalytic function of this wettability changing layer. It was. In addition, it was found that by using a silane coupling agent as a ligand, the life characteristics of the EL element can be improved by improving the adhesion between the materials in the light emitting layer and between the light emitting layer and the first electrode layer or the hole injection transport layer. In addition, it was found that by using a silane coupling agent as a ligand, it is possible to insolubilize the light emitting layer with respect to a solvent and to introduce coating in a subsequent step of the light emitting layer forming step.

That is, the present invention provides a wettability change layer forming step of forming a wettability change layer in which a wettability change layer is formed on a substrate on which a first electrode layer is formed, and the wettability is changed by the action of the photocatalyst according to energy irradiation, and the wettability change. The pattern of the wettability change pattern for forming a wettability change pattern including a lyophilic region and a liquid repellent region on the surface of the wettability change layer by irradiating the layer with a pattern on the wettability change layer, and on the wettability change layer having a wettability change pattern formed thereon, A light emitting layer forming step of coating a light emitting layer forming coating solution containing a quantum dot having a ligand disposed around the same and forming a light emitting layer on the lyophilic region is provided.

According to the present invention, it is possible to easily pattern the light emitting layer by forming the wettability change pattern by irradiating the wettability change layer with a patterned energy and using the wettability difference of the wettability change pattern.

In addition, the present invention provides a wettability changing layer forming step of forming a wettability changing layer whose wettability is changed by the action of a photocatalyst according to energy irradiation on a substrate on which a first electrode layer is formed, and light containing at least a photocatalyst on a substrate. The wettability changing layer is disposed by arranging a photocatalyst treatment layer gas having a catalyst treatment layer on the wettability changing layer with a gap in which the action of the photocatalyst due to energy irradiation can be applied, and then irradiating energy in a patterned manner. For forming a lightness change pattern for forming a wettability change pattern including a lyophilic region and a liquid repellent region on a surface thereof, and a light emitting layer for forming a light emitting layer containing a quantum dot having a ligand disposed around the wettability change layer having a wettability change pattern formed thereon; And a light emitting layer forming step of applying a coating liquid to form a light emitting layer on the lyophilic region. A manufacturing method of an EL device is provided.

According to the present invention, it is possible to easily pattern a light emitting layer by forming a wettability change pattern by irradiating the wettability change layer with a pattern energy through a photocatalyst treatment layer, and using the wettability difference of this wettability change pattern. In addition, since the photocatalyst is contained in the photocatalyst treatment layer and the photocatalyst treatment layer gas having the photocatalyst treatment layer is removed from the wettability change layer after the wettability change pattern forming process, the wettability change layer contains the photocatalyst. Instead, the barrier at the interface between the wettability changing layer and the light emitting layer can be reduced, thereby improving the light emitting characteristics.

In the said invention, it is preferable that the said ligand is a silane coupling agent. This is because the light emitting layer can be cured by using the coating liquid for forming the light emitting layer containing the silane coupling agent, the stability of the quantum dots in the light emitting layer can be improved, and the lifespan characteristics can be improved. In addition, since the silane coupling agent is relatively easy in molecular design, the life characteristics can be improved by using a silane coupling agent having a functional group exhibiting various functionalities. In addition, when a wettability change layer contains organopolysiloxane as mentioned later, the organopolysiloxane in a wettability change layer couple | bonds with a 1st electrode layer, and the silane coupling agent in a light emitting layer couple | bonds with a wettability change layer, and a 1st electrode layer And the adhesion between the wettability-changing layer and the light emitting layer can be improved.

In the above case, the silane coupling agent is YnSiX (4-n), wherein Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, X represents an alkoxyl group, an acetyl group or a halogen, n Is an integer of 0 to 3). Since the silicon compound is relatively easy in molecular design, the degree of condensation and the like can be controlled by appropriately selecting X and Y. Thereby, stability of the quantum dot in a light emitting layer can be made desired.

In addition, in the above case, the silane coupling agent is YnSiX (4-n), wherein Y represents electron transportability bonded through a functional group, direct, vinyl group, or phenyl group, indicating hole transportability directly bonded through a vinyl group or a phenyl group. Silicon represented by a functional group or a functional group capable of exhibiting both hole transportability and electron transportability bonded directly through a vinyl group or a phenyl group, X represents an alkoxyl group, an acetyl group or a halogen, and n is an integer of 0 to 3). It may be a compound. Since the silicon compound is relatively easy in molecular design, it can be set as having a functional group which shows various functionalities, and can improve the life characteristic.

In addition, in the above-mentioned case, it is preferable to apply | coat and apply the coating liquid for light emitting layer formation in the said light emitting layer formation process, and to harden | cure. This is because the stability of the quantum dots in the light emitting layer can be improved as described above, and the lifespan characteristics can be improved. In addition, when a wettability change layer contains organopolysiloxane as mentioned later, the organopolysiloxane in a wettability change layer couple | bonds with a 1st electrode layer, and the silane coupling agent in a light emitting layer couple | bonds with a wettability change layer, and a 1st electrode layer This is because the adhesion between the wettability-changing layer and the light emitting layer can be improved. Furthermore, the thermal stability (Tg: glass transition temperature) of a light emitting layer can also be improved.

Moreover, in this invention, it is preferable that the said quantum dot has the core part containing semiconductor microparticles | fine-particles, and the shell part which coat | covers the said core part and consists of a material with a bandgap larger than the said semiconductor microparticles | fine-particles. It is because quantum dots are stabilized by setting it as such a structure.

In the present invention, the light-emitting layer-forming coating liquid may further contain any one or more of a hole transport material and an electron transport material. By combining these materials with the quantum dots, the manufacturing process of the EL element can be simplified, or the energy transfer of excitons generated by charge transport to the light emitting layer and recombination of holes and electrons can be performed efficiently, This is because the lifespan characteristics can be improved.

Moreover, in this invention, it is preferable that the coating method of the said coating liquid for light emitting layer formation is a discharge method. This is because in the ejection method, a highly precise pattern can be formed using the wettability change pattern.

In the present invention, the wettability changing layer is YnSiX (4-n), wherein Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, and X represents an alkoxyl group, an acetyl group or a halogen And n is an integer of 0 to 3), and preferably contains one or two or more hydrolyzed condensates or copolyhydrolyzed condensates of organopolysiloxane. Organopolysiloxanes as described above are preferred because the materials used in the wettability changing layer require binding energy such that the wettability is changed by the action of the photocatalyst and is not decomposed by the action of the photocatalyst.

In addition, the present invention is formed on the substrate, the first electrode layer formed in a pattern on the substrate, and the first electrode layer, the wettability is changed by the action of the photocatalyst by energy irradiation, the pattern of the first electrode layer A wettability change layer having a wettability change pattern comprising a lyophilic region containing a polysiloxane corresponding to and a liquid repellent region containing an organopolysiloxane containing fluorine corresponding to an opening of a pattern of the first electrode layer, and the wettability A quantum dot having a light emitting layer formed on the lyophilic region of the change layer and a second electrode layer formed on the light emitting layer, and having a silane coupling agent disposed thereon, is used for the light emitting layer.

Here, fluorine has very low surface energy. In the present invention, since the lyophilic region on the surface of the wettability changing layer contains polysiloxane, and the liquid repellent region contains organopolysiloxane containing fluorine, the lyophilic region and the liquid repellent region are compared with each other. It can be said that the critical surface tension becomes larger. According to the present invention, the light emitting layer can be formed only on the lyophilic region by using the difference in the wettability between the liquid repellent region and the lyophilic region, and the EL element can be easily patterned.

In addition, since quantum dots with a silane coupling agent are disposed around the light emitting layer, the light emitting layer can be cured, and the stability of the quantum dots in the light emitting layer can be improved, and the life characteristics can be improved. Do. In addition, since the silane coupling agent is relatively easy in molecular design, it is possible to improve the life characteristics by using a silane coupling agent having a functional group exhibiting various functionalities. In addition, since the wettability changing layer contains an organopolysiloxane, the organopolysiloxane in the wettability changing layer is bonded to the first electrode layer, and the silane coupling agent in the light emitting layer is bonded to the wettability changing layer, thereby providing the first electrode layer and the wettability changing layer. The adhesion of the light emitting layer can be improved.

In the said invention, it is preferable that the said light emitting layer contains the hydrolysis-condensation product of the said silane coupling agent, and is hardened | cured. As a result, as described above, the stability of the quantum dots in the light emitting layer can be improved, and the lifespan characteristics can be improved. In addition, the adhesion between the first electrode layer, the wettability changing layer, and the light emitting layer can be improved. Furthermore, the thermal stability (Tg: glass transition temperature) of a light emitting layer can also be improved.

In the above case, the hydrolysis condensate of the silane coupling agent is YnSiX (4-n), wherein Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, and X represents an alkoxyl group, an acetyl group or Organopolysiloxane, which is one or two or more hydrolytic condensates or cohydrolytic condensates of a silicon compound represented by halogen, and n is an integer of 0 to 3). Since such an organopolysiloxane is relatively easy in molecular design, the degree of condensation and the like can be controlled by appropriately selecting X and Y. Thereby, stability of the quantum dot in a light emitting layer can be made desired.

In addition, in the above case, the hydrolysis-condensation product of the silane coupling agent is YnSiX (4-n), wherein Y is directly through a functional group, a direct group, a vinyl group, or a phenyl group, which exhibits hole transportability bonded through a vinyl group or a phenyl group. A functional group which shows the bonded electron transport property, or a functional group which can represent both the hole transport property and the electron transport property which were couple | bonded directly through the vinyl group or the phenyl group, X represents an alkoxyl group, an acetyl group, or a halogen, n is an integer of 0-3 The organopolysiloxane which is 1 type, or 2 or more types of hydrolysis-condensation product or co-hydrolysis-condensation product of the silicon compound represented by) may be sufficient. Since such an organopolysiloxane is relatively easy in molecular design, it can be made to have a functional group which shows various functionalities, and can improve life characteristics.

Moreover, in this invention, it is preferable that the said quantum dot has the core part containing semiconductor microparticles | fine-particles, and the shell part which coat | covers the said core part and consists of a material with a bandgap larger than the said semiconductor microparticles | fine-particles. It is because quantum dots are stabilized by setting it as such a structure.

According to the present invention, the wettability changing layer is patterned with energy to form a wettability change pattern, and the light emitting layer can be easily patterned by utilizing the difference in wettability of the wettability change pattern.

According to the present invention, it is possible to provide a method for producing an EL element which can easily pattern a light emitting layer containing quantum dots.

EMBODIMENT OF THE INVENTION Hereinafter, the EL element of this invention and its manufacturing method are demonstrated in detail.

A. Manufacturing Method of EL Device

The manufacturing method of the EL element of this invention can be classified into two embodiment according to the structure of a wettability change layer, and the wettability change pattern formation process. Hereinafter, it classifies into each embodiment and demonstrates.

I. First Embodiment

The first embodiment of the method for manufacturing an EL device of the present invention is a wettability which includes a photocatalyst on a substrate on which a first electrode layer is formed, and forms a wettability changing layer whose wettability is changed by the action of the photocatalyst according to energy irradiation. A wettability change pattern forming step of forming a wettability change pattern including a lyophilic region and a liquid-repellent region on the surface of the wettability-changing layer by irradiating the changeable layer formation process with the wettability-modifying layer in a pattern shape; It has a light emitting layer formation process which forms the light emitting layer by apply | coating the coating liquid for light emitting layer formation containing the quantum dot in which the ligand was arrange | positioned around the area | region.

The manufacturing method of the EL element of this embodiment is demonstrated, referring drawings.

1 is a process chart showing an example of a method of manufacturing the EL device of the present embodiment. First, the first electrode layer 2 is formed in a pattern form on the substrate 1, the insulating layer 3 is formed in the opening of the pattern of the first electrode layer 2, and the first electrode layer 2 and the insulating layer are formed. The wettability changing layer 4 is formed on (3) (FIG. 1 (a), a wettability changing layer formation process).

Subsequently, the wettability changing layer 4 is irradiated with ultraviolet rays 12 through the photomask 11 (FIG. 1B). By irradiation of the ultraviolet ray 12, the wettability changes in the irradiation part of the wettability change layer 4 from the action of the photocatalyst contained in the wettability change layer 4 so that the contact angle with a liquid may fall (FIG. 1 (c)). ). The region whose wettability has changed so that the contact angle with this liquid falls is set to the lyophilic region 5. In the unirradiated portion, the wettability is not changed. The region where this wettability is not changed is referred to as the liquid repellent region 6. As a result, a wettability change pattern including the lyophilic region 5 and the liquid repellent region 6 is formed on the wettability changing layer 4 surface. 1 (b) and (c) show a wettability change pattern forming process.

The wettability changing layer 4 contains a photocatalyst, and the wettability is changed by the action of the photocatalyst according to the energy irradiation. In the wettability-changing layer 4, the wettability-changing layer 4 and the non-irradiating portion are liquid repellent regions 6 There is a difference in wettability.

Subsequently, using this wettability difference, the coating liquid for forming a light emitting layer is applied onto the wettability change pattern including the lyophilic region 5 and the liquid repellent region 6, and the light emitting layer 7 is disposed only on the lyophilic region 5. ) (FIG. 1 (d), the light emitting layer forming step).

The quantum dot 22 in which the ligand 21 was arrange | positioned around the luminescent layer forming coating liquid as shown in FIG. 2 is used. That is, the ligand 21 is affixed to the surface of the quantum dot 22, and the quantum dot 22 with this ligand 21 attached to the surface is used for the coating liquid for light emitting layer formation.

Next, the second electrode layer 8 is formed on the light emitting layer 7 (FIG. 1E, the second electrode layer forming step). At this time, for example, when the second electrode layer 8 is used as a transparent electrode, an EL element of a top emission type is obtained. When the first electrode layer 2 is used as a transparent electrode, an EL element of a bottom emission type is obtained. Lose.

In the present embodiment, the wettability change layer containing the photocatalyst is irradiated with a pattern to form energy, thereby forming a wettability change pattern including a lyophilic region and a liquid repellent region on the wettability change layer surface. Further, the light emitting layer is patterned by using the wettability changing pattern formed on the surface of the wettability changing layer. Therefore, it is possible to easily pattern the light emitting layer without the need for complicated patterning process or expensive vacuum equipment.

In addition, in this embodiment, it is preferable that the ligand adhering to the surface of a quantum dot is a silane coupling agent as mentioned later. Thereby, a light emitting layer can be made hard, the stability of the quantum dot in a light emitting layer can be made favorable, and a lifetime characteristic can be improved. In addition, since the silane coupling agent is relatively easy in molecular design, it is possible to improve the life characteristics by using a silane coupling agent having a functional group exhibiting various functionalities.

In addition, as mentioned later, it is preferable that a wettability change layer contains organopolysiloxane. In this case, the organopolysiloxane in the wettability changing layer is bonded to the first electrode layer, and the silane coupling agent in the light emitting layer is bonded to the wettability changing layer, whereby the adhesion between the first electrode layer, the wettability changing layer and the light emitting layer can be improved. Thereby, it is possible to prevent the deterioration of the life characteristics due to the interlayer peeling or the like during EL element driving or the like.

Hereinafter, each process in the manufacturing method of an EL element is demonstrated.

1. Wetability change layer forming process

The wettability changing layer forming process in this embodiment is a process of forming the wettability changing layer in which wettability is changed on the board | substrate with which the 1st electrode layer was formed, and a wettability is changed by the action of the photocatalyst by energy irradiation.

Hereinafter, the wettability changing layer, the method of forming the wettability changing layer, the substrate, and the first electrode layer will be described.

(1) wettability changing layer

The wettability changing layer in the present embodiment is not particularly limited as long as the wettability changing layer contains a photocatalyst and the wettability is changed by the action of the photocatalyst according to energy irradiation. For example, the wettability changing layer may be a single layer containing a photocatalyst and whose wettability is changed by the action of the photocatalyst according to energy irradiation (first embodiment), the layer containing the photocatalyst, and the energy The layer which changes wettability by the action of a photocatalyst may be laminated (2nd aspect). Hereinafter, each aspect is demonstrated.

(i) First aspect

The wettability changing layer of this embodiment is a single layer containing a photocatalyst and whose wettability is changed by the action of the photocatalyst by energy irradiation. Since the wettability change layer changes wettability by the action of the photocatalyst contained in the wettability change layer itself, the wettability change layer can form a wettability change pattern efficiently.

The wettability changing layer of the present embodiment is not particularly limited as long as the wettability changing layer contains a photocatalyst and the wettability is changed by the action of the photocatalyst according to the energy irradiation, and is usually a material whose wettability is changed by the action of the photocatalyst and the photocatalyst. It contains.

As the photocatalyst, for example, titanium dioxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), bismuth oxide ( Bi ₂ O ₃ ) and iron oxide (Fe ₂ O ₃ ). These photocatalysts may be used individually by 1 type, and may mix and use 2 or more types.

Among these, titanium dioxide is preferably used because of its high bandgap energy, chemical stability, no toxicity, and easy availability. Titanium dioxide has anatase type and rutile type, and both can be used. Especially, anatase type titanium dioxide is preferable. The anatase titanium dioxide has an excitation wavelength of 380 nm or less.

As anatase type titanium dioxide, for example, anatase type titania sol of hydrochloric acid bridge type (Ishihara Sangyo Co., Ltd. make STS-02 (average particle diameter: 7 nm), Ishihara Sangyo Co., Ltd. make ST-K01), nitric acid bridge type Anatase type titania sol (TA-15 (average particle diameter: 12 nm) by Nissan Chemical Industries, Ltd.) etc. are mentioned.

The smaller the particle diameter is, the more effectively the photocatalytic reaction occurs. Therefore, it is preferable that the particle size of the photocatalyst is small. Specifically, the average particle diameter of the photocatalyst is preferably 50 nm or less, particularly preferably 20 nm or less.

The photo-catalytic action mechanism, represented by the titanium dioxide include, but are not clear, by the photocatalyst by irradiation of the energy generated by oxidation and reduction reactions, the super-oxide radicals (and O ₂ ^-) or hydroxyl radical (and OH) It is thought that active oxygen species such as these are generated and the generated active oxygen species change the chemical structure of organic matter. In this embodiment, this active oxygen species is considered to have an effect on the organic matter in the wettability changing layer.

Content of the photocatalyst in a wettability change layer can be set in the range of 5 mass%-90 mass%, Preferably it exists in the range of 20 mass%-70 mass%.

In addition, content of a titanium dioxide, a crystalline form, etc. in a wettability change layer can be confirmed using X-ray photoelectron spectroscopy, Rutherford backscattering spectroscopy, nuclear magnetic resonance spectroscopy, or mass spectrometry, or a combination of these methods.

In addition, the material whose wettability is changed by the action of the photocatalyst according to energy irradiation is not particularly limited as long as it has a main chain that is hardly deteriorated and decomposed by the action of the photocatalyst. As such a material, for example, (1) organopolysiloxane which hydrolyzes and polycondenses chloro or alkoxysilane or the like by a sol-gel reaction or the like and exhibits great strength, and (2) organo-crosslinked reactive silicone having excellent water and oil repellency. Organopolysiloxanes, such as polysiloxane, are mentioned.

In the case of the above (1),

YnSiX (4-n)

(Wherein Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, X represents an alkoxyl group, an acetyl group or a halogen and n is an integer of 0 to 3)

Organopolysiloxane which is 1 type, or 2 or more types of hydrolysis-condensation product or co-hydrolysis-condensation product of the silicon compound represented by is used preferably. It is preferable that carbon number of the group represented by Y exists in the range of 1-20, and it is preferable that the alkoxyl group represented by X is a methoxy group, an ethoxy group, a propoxy group, butoxy group. As a silicon compound represented by the said chemical formula, the thing specifically described in Unexamined-Japanese-Patent No. 2000-249821 can be used.

In particular, polysiloxanes containing a fluoroalkyl group can be preferably used. Examples of the polysiloxane containing a fluoroalkyl group include one or two or more hydrolysis condensates or cohydrolysis condensates of the fluoroalkylsilanes described in JP-A-2000-249821. Generally what is known as a fluorine-type silane coupling agent can be used.

Since the liquid repellency of the wettability-changing layer is greatly improved by using polysiloxane containing a fluoroalkyl group, the wettability can be prevented from forming the light emitting layer in the liquid-repellent region where the wettability is not changed, and the wettability is reduced so that the contact angle with the liquid is lowered. It is possible to form the light emitting layer only on the changed lyophilic region.

In addition, the polysiloxane containing a fluoroalkyl group in a wettability change layer can be confirmed using X-ray photoelectron spectroscopy, Rutherford backscattering spectroscopy, nuclear magnetic resonance spectroscopy, or mass spectrometry.

Moreover, as said reactive silicone of said (2), the compound which has frame | skeleton represented by a following formula is mentioned.

Provided that n is an integer of 2 or more, R ¹ and R ² are substituted or unsubstituted alkyl, alkenyl, aryl or cyanoalkyl groups having 1 to 10 carbon atoms, and 40% or less of the total is molar ratio of vinyl, phenyl, Phenyl halide. In addition, it is preferable that R ¹ and R ² be a methyl group because the surface energy is the smallest, and it is more preferable that the methyl group is 60% or more in molar ratio. The chain terminal or side chain has a reactive group such as at least one or more hydroxyl groups in the molecular chain.

It is also possible to mix with the organopolysiloxane described above a stable organosilicon compound which does not undergo a crosslinking reaction such as dimethylpolysiloxane.

Thus, although various materials, such as organopolysiloxane, can be used for a wettability change layer, it is preferable that a wettability change layer contains fluorine especially. In this case, it is preferable that the fluorine content on the surface of this wettability changing layer is reduced compared with before energy irradiation by the action of the photocatalyst according to energy irradiation.

Since fluorine has a very low surface energy, the surface of a fluorine-containing material has a smaller critical surface tension. Therefore, compared with the critical surface tension of the surface of the part with much fluorine content, the critical surface tension of the part with little fluorine content becomes large.

In the wettability changing layer as described above, the wettability change includes a portion having a low fluorine content (liquid lyophilic region) that is an energy irradiated portion and a portion having a high fluorine content (a liquid soluble region) that is an unirradiated portion by energy irradiation. This is because a pattern can be formed. Thus, when a wettability change layer contains fluorine, it is advantageous for formation of a wettability change pattern.

In addition, the wettability changing layer may contain, in addition to the above-mentioned materials, for example, the same surfactants, additives and the like as described in JP-A-2000-249821.

Such a wettability changing layer can be formed by dissolving or dispersing the above-mentioned material together with other additives in a solvent as needed to produce a coating solution for forming a wettability changing layer, and applying the coating solution for forming a wettability changing layer onto an electrode layer. have.

At this time, as a solvent which can be used for the coating liquid for wettability-changing layer formation, it will mix with the above-mentioned material etc., and if it does not affect patterning characteristic by cloudy or other phenomenon, it will not specifically limit. As such a solvent, For example, alcohols, such as methanol, ethanol, isopropanol, butanol, acetone, acetonitrile, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, diethyl Glycol monomethyl ether, diethyl glycol monoethyl ether, diethyl glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, methyl acetate, ethyl acetate, butyl acetate, toluene, Xylene, methyl lactate, ethyl lactate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, dimethylformamide, dimethyl sulfoxide, dioxane, ethylene glycol, hexamethyl phosphate triamide, pyridine, tetrahydrofuran , N-methylpyrrolidinone and the like have. These solvents can be used in mixture of 2 or more type.

Moreover, as a coating method of the coating liquid for wettability changing layer formation, for example, a spin coating method, the inkjet method, the casting method, the LB method, the dispenser method, the microgravure coating method, the gravure coating method, the bar coating method, the roll coating method, The wire bar coating method, the dip coating method, the flexographic printing method, the offset printing method, the screen printing method, etc. are mentioned.

The coating film may be dried after application of the coating solution for forming the wettability changing layer. As a drying method, if it is a method which can form a uniform wettability change layer, it will not specifically limit, For example, a hotplate, an infrared heater, oven, etc. can be used.

The film thickness of the wettability changing layer is not particularly limited as long as the wettability changing pattern can be formed and the film thickness does not inhibit the transport of holes or electrons. It is preferable that it is 10 nm-500 nm specifically, and it is especially preferable to exist in the range of 10 nm-200 nm, especially 10 nm-100 nm. If the wettability changing layer is too thin, it is difficult to form a film uniformly. On the contrary, if the wettability changing layer is too thick, there is a possibility of inhibiting the movement of holes or electrons.

(ii) a second aspect

The wettability changing layer of this embodiment is a layer in which a layer containing a photocatalyst and a layer which is wettable or changed by the action of the photocatalyst according to energy irradiation (hereinafter sometimes referred to as a layer whose wettability changes) are laminated. Since the wettability changing layer is divided into layers according to functions, the layer structure, the combination of materials, and the like can be easily changed. Hereinafter, each structure of a wettability change layer is demonstrated.

(Layer containing photocatalyst)

The layer containing the photocatalyst used in this embodiment is not particularly limited as long as it contains the photocatalyst and changes the wettability of the layer in which the wettability of the photocatalyst in this layer is laminated is changed.

In addition, the layer containing the photocatalyst may further contain a binder. This makes it easy to form a film. The binder used in the present embodiment is not particularly limited as long as the main skeleton has a high binding energy that is not decomposed by photoexcitation of the photocatalyst. For example, alkylsilicates can be used. Examples of the alkyl silicates include compounds represented by the general formula SinO _{n -1} (OR) _{2n + 2} (wherein Si represents silicon, O represents oxygen, and R represents an alkyl group). N is preferably in the range of 1 to 6, and R is preferably an alkyl group having 1 to 4 carbon atoms in terms of a large proportion of silicon. Moreover, the material whose wettability changes by the action of the photocatalyst by the energy irradiation described in the said 1st aspect can also be used.

In addition, the wettability of the surface of the layer containing the photocatalyst may be lyophilic or liquid repellent.

The thickness of the layer containing the photocatalyst is not particularly limited as long as it does not hinder the movement of holes or electrons. Specifically, the thickness of the layer containing the photocatalyst is preferably 10 nm to 500 nm, and particularly 10 nm to 200 nm, particularly 10 nm to. It is preferable to exist in the range of 100 nm. It is because it may become difficult to change the wettability of the layer from which wettability changes when the layer containing a photocatalyst is too thin. On the contrary, if the layer containing the photocatalyst is too thick, there is a possibility of inhibiting the movement of holes or electrons.

(Layer in which wettability is changed)

The layer whose wettability is changed in the present embodiment is not particularly limited as long as the wettability is changed by the action of the photocatalyst according to energy irradiation, and is usually a material whose wettability is changed by the action of the photocatalyst according to energy irradiation. It is to contain. In addition, about the material whose wettability changes by the action of the photocatalyst by energy irradiation, since it is the same as that of what was described in the said 1st aspect, the description here is abbreviate | omitted.

Moreover, surfactant, an additive, etc. can be contained in the layer which changes wettability similarly to the said 1st aspect.

The thickness of the layer in which the wettability is changed is not particularly limited as long as it is possible to form a wettability change pattern and does not inhibit the transport of holes or electrons. Specifically, the thickness is preferably 0.5 nm to 20 nm, and among them, 0.5 nm. It is preferable to exist in the range of -10 nm. It is because there exists a possibility that the difference in wettability may not express clearly if a wettability change layer is too thin. On the contrary, if the wettability-changing layer is too thick, there is a possibility of inhibiting the transport of holes or electrons.

(2) substrate

The substrate used for this embodiment may or may not have transparency. For example, in the EL element shown in Fig. 1E, the substrate 1 preferably has transparency. On the other hand, for example, in the EL element shown in Fig. 1E, when the top emission type is used, transparency is not required for the substrate 1. For example, when taking out light from both surfaces in the EL element shown to Fig.1 (e), it is preferable that the board | substrate 1 has transparency.

As the substrate having transparency, an inorganic material such as glass, a transparent resin, or the like can be used.

Although it will not specifically limit, if it can shape | mold in a film form as said transparent resin, It is preferable that transparency is high and solvent resistance and heat resistance are comparatively high. As such a transparent resin, for example, polyether sulfone, polyethylene terephthalate (PET), polycarbonate (PC), polyether ether ketone (PEEK), polyvinyl fluoride (PFV), polyacrylate (PA), poly Propylene (PP), polyethylene (PE), amorphous polyolefin or fluorine resin.

(3) first electrode layer

The first electrode layer used in the present embodiment may be an anode or a cathode. Generally, when manufacturing an EL element, since laminating from the anode side can stably produce the EL element, it is preferable that the first electrode layer is an anode.

As the anode, a conductive material having a large work function is preferably used so that holes are easily injected. On the other hand, a conductive material having a small work function is preferably used for the cathode so as to easily inject electrons. Although a metal material is generally used as an electroconductive material, organic substance or an inorganic compound can also be used. In addition, a some material can also be mixed and used for a 1st electrode layer.

In addition, the first electrode layer may or may not have transparency, and is appropriately selected depending on the light extraction surface. For example, in the EL element shown in Fig. 1E, it is preferable that the first electrode layer 2 has transparency in the case of the bottom emission type. On the other hand, for example, in the EL element shown in Fig. 1E, transparency is not required for the first electrode layer 2 when it is a top emission type. For example, in the case of extracting light from both surfaces in the EL element shown in Fig. 1E, it is preferable that the first electrode layer 2 has transparency.

As an electroconductive material which has transparency, In-Zn-O (IZO), In-Sn-O (ITO), Zn-O-Al, Zn-Sn-O etc. can be illustrated as a preferable thing. Moreover, when transparency is not required, a metal can be used as a conductive material, Specifically, Au, Ta, W, Pt, Ni, Pd, Cr or Al alloy, Ni alloy, Cr alloy, etc. are mentioned.

Regardless of which of the anode and the cathode, the first electrode layer is preferably relatively small in resistance.

As the film forming method of the first electrode layer, a general electrode film forming method can be used, and a sputtering method, an ion plating method, a vacuum vapor deposition method and the like can be mentioned. Moreover, the photolithographic method is mentioned as a patterning method of a 1st electrode layer.

2. Wetability change pattern forming process

The wettability change pattern forming step in this embodiment is a step of forming a wettability change pattern including a lyophilic region and a liquid-repellent region on the surface of the wettability change layer by energizing the wettability change layer in a pattern form.

The wavelength of light used for energy irradiation is usually set in the range of 450 nm or less, and preferably in the range of 380 nm or less. This is because, as described above, the preferred photocatalyst used in the wettability changing layer is titanium dioxide, and light having the above wavelength is preferable as energy for activating the photocatalytic action by the titanium dioxide.

As a light source which can be used for energy irradiation, a mercury lamp, a metal halide lamp, a xenon lamp, an excimer lamp, and various other light sources are mentioned.

In addition, as a method of irradiating energy on a pattern, in addition to the method of irradiating a pattern through a photomask using these light sources, the method of drawing irradiation on a pattern using lasers, such as an excimer and a YAG, can also be used.

The irradiation amount of energy at the time of energy irradiation is made into the irradiation amount required in order to change the wettability of the surface of a wettability change layer by the action of the photocatalyst in a wettability change layer.

At this time, it is preferable to perform energy irradiation while heating the wettability changing layer. It is because a sensitivity can be raised and a wettability can be changed efficiently. Specifically, heating in the range of 30 ° C to 80 ° C is preferable.

The energy irradiation method is not particularly limited as long as it is a method capable of changing the wettability of the wettability changing layer. In addition, irradiation of energy can also be performed using the mask in which the target pattern was formed, for example, a photomask. It is because it becomes possible to irradiate energy to the target pattern shape by this, and can change the wettability of a wettability change layer to a pattern shape. In this case, the type of mask to be used is not particularly limited as long as energy can be irradiated onto a target pattern, and may be a photomask or the like having a light shielding portion formed on a material that transmits energy, and a hole portion is formed on the target pattern. It may be a shadow mask or the like. Moreover, as a material of these masks, an organic substance, such as an inorganic substance, such as a metal, glass, a ceramic, or a plastic, etc. are mentioned specifically ,.

As an energy irradiation direction, it can carry out from any direction of a board | substrate side and a wettability change layer side. When using a photomask, energy is irradiated from the side in which the photomask is arrange | positioned.

In the present invention, the lyophilic region refers to a region having a smaller contact angle with the liquid than the liquid repellent region, and is a region having good wettability with respect to the coating liquid for forming the light emitting layer. The liquid-repellent region refers to a region in which the contact angle with the liquid is larger than that of the lyophilic region, and the wettability to the coating liquid for forming the light emitting layer is deteriorated. In addition, when the contact angle with the liquid is 1 ° or more lower than the contact angle with the liquid in the adjacent region, the liquid-repellent region or the liquid-repellent region when the contact angle with the liquid is 1 ° or more higher than the contact angle with the liquid in the adjacent region. do.

In the liquid repellent region, it is preferable that the contact angle with respect to the liquid having a surface tension equivalent to that of the coating liquid for forming the light emitting layer or the like exceeds 21 °, more preferably 30 ° or more, even more preferably 40 ° or more. to be. Since the liquid repellent region is a portion where liquid repellency is required, if the contact angle with the liquid is too small, the liquid repellency is not sufficient, and there is a possibility that a coating liquid for forming a light emitting layer may be attached to the liquid repellent region.

In the lyophilic region, the contact angle with respect to a liquid having a surface tension equivalent to that of the coating liquid for forming the light emitting layer or the like is preferably 20 ° or less, more preferably 15 ° or less, even more preferably 10 ° or less. to be. If the contact angle with the liquid is too high, the coating liquid for forming the light emitting layer may be difficult to wet, and the light emitting layer may be lacking.

In addition, the contact angle with liquid measured the contact angle with the liquid which has a various surface tension using a contact angle measuring device (type CA-Z by Kyowa Kaimen Kagaku Co., Ltd.). 2), and the result can be calculated | required by graphing. In this measurement, the wetness index standard liquid manufactured by Junsu Chemical Co., Ltd. is used as a liquid having various surface tensions.

In the case where the wettability-changing layer contains fluorine, the fluorine content in the lyophilic region is preferably 50 or less, more preferably 20 or less, even more preferably 10 or less when the fluorine content in the liquid repellent region is 100. . In addition, this ratio is based on weight. By making the ratio of fluorine content into the said range, a big difference can be produced in the wettability of a liquid repellent region and a lyophilic region. Therefore, when the light emitting layer is formed on the wettability changing layer as described above, the light emitting layer can be formed precisely only in the lyophilic region having a low fluorine content, so that a highly accurate light emitting layer pattern can be obtained.

In addition, the measurement of fluorine content can use various methods generally performed, for example, X-ray photoelectron spectroscopy (also called Electron Spectroscopy for Chemical Analysis), fluorescence X-ray analysis, A method capable of quantitatively measuring the amount of fluorine on the surface, such as mass spectrometry, can be used.

3. Light emitting layer forming process

The light emitting layer formation process in this embodiment is a process of apply | coating the light emitting layer formation coating liquid containing the quantum dot in which the ligand was arrange | positioned around the said lipophilic area | region, and forming a light emitting layer.

The light emitting layer formation process in this embodiment may be the process (3rd aspect) of forming a single light emitting layer using the light emitting layer formation coating liquid containing the quantum dot in which the ligand was arrange | positioned around, and a ligand The step (fourth aspect) of forming a single light emitting layer using the quantum dot arrange | positioned and the coating liquid for light emitting layer formation containing any one or more of a hole transport material and an electron transport material may be sufficient, and a ligand is arrange | positioned around The process (5th aspect) of forming a light emitting layer and a positive hole transport layer collectively using the coating liquid for light emitting layer formation containing a quantum dot and a hole transport material may be sufficient. Hereinafter, each aspect is demonstrated.

(1) Third aspect

The light emitting layer formation process in this aspect is a process of apply | coating the light emitting layer forming coating liquid containing the quantum dot by which the ligand was arrange | positioned on the said lyophilic region, and forming a single light emitting layer. Hereinafter, the coating liquid for light emitting layer formation and the formation method of a light emitting layer are demonstrated.

(i) Coating solution for forming light emitting layer

The coating liquid for light emitting layer formation used for this aspect contains the quantum dot by which the ligand was arrange | positioned around it, and the quantum dot by which the ligand was arrange | positioned normally is disperse | distributed to the solvent. Hereinafter, each structure of the coating liquid for light emitting layer formation is demonstrated.

(Quantum dot)

The quantum dots used in this embodiment are not particularly limited as long as they emit fluorescence or phosphorescence. Especially, it is preferable that a quantum dot contains what is called a compound semiconductor. As the compound semiconductor, for example, a compound of group IV, a compound of group I-VII, a compound of group II-VI, a compound of group II-V, a compound of group III-VI, a compound of group III-V, IV-VI The compound of a group, the compound of group I-III-VI, the compound of group II-IV-VI, the compound of group II-IV-V, etc. are mentioned. Specifically, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, GaSe, InN, InP, InAs, InSb, TlN, TlP , TlAs, TlSb, PbS, PbSe, PbTe or mixtures thereof. Especially, CdSe is preferable from a viewpoint of versatility and an optical characteristic.

A quantum dot may contain only the core part containing a semiconductor fine particle, and may have a core part containing a semiconductor fine particle, and the shell part which coat | covers a core part and consists of a material with a bandgap larger than a semiconductor fine particle. Among these, it is preferable that a quantum dot has the said core part and the said shell part. That is, it is preferable that the quantum dots have a core shell structure and are core shell type quantum dots. This is because the stability of the quantum dots is improved.

As semiconductor microparticles | fine-particles used for a core part, microparticles | fine-particles of the said compound semiconductor are used preferably.

The material used for the shell portion is not particularly limited as long as the material has a band gap larger than that of the semiconductor fine particles, but is preferably the compound semiconductor similarly to the semiconductor fine particles. In this case, the compound semiconductor used for the shell portion may be the same as or different from the compound semiconductor used for the core portion.

Examples of the core-shell quantum dots include CdSe / CdS, CdSe / ZnS, CdTe / CdS, InP / ZnS, GaP / ZnS, Si / ZnS, InN / GaN, InP / CdSSe, InP / ZnSeTe, GaInP / ZnSe, GaInP / ZnS, Si / AlP, InP / ZnSTe, GaInP / ZnSTe, GaInP / ZnSSe and the like. Among these, CdSe / ZnS is preferable from the viewpoint of versatility and optical characteristics.

Moreover, as a shape of a quantum dot, spherical shape, rod shape, disk shape, etc. are mentioned, for example.

In addition, the shape of a quantum dot can be confirmed with a transmission electron microscope (TEM).

It is preferable that the particle diameter of a quantum dot is less than 20 nm, and it is especially preferable to exist in the range of 1 nm-15 nm, especially the range of 1 nm-10 nm. This is because if the particle diameter of the quantum dots is too large, the quantum size effect may not be obtained.

Since the quantum dots exhibit different emission spectra depending on their particle diameters, the particle diameter of the quantum dots is appropriately selected according to the desired color. For example, in the case of the core-shell quantum dot containing CdSe / ZnS, the emission spectrum shifts to the longer wavelength side as the particle size increases, and when the particle diameter is 5.2 nm, red color is displayed. When the particle diameter is 1.9 nm, blue color is used. Indicates.

Moreover, it is preferable that the particle size distribution of a quantum dot is comparatively narrow.

In addition, the particle diameter of a quantum dot can be confirmed by a transmission electron microscope (TEM), a powder X-ray diffraction (XRD) pattern, or a UV / Vis absorption spectrum.

As content in the coating liquid for light emitting layer formation of the quantum dot arrange | positioned around a ligand, when the total solid in the coating liquid for light emitting layer forming is 100 mass%, it is preferable to exist in the range of 50 mass%-100 mass%, and especially 60 It is preferable to exist in the range of mass%-100 mass%. It is because there exists a possibility that sufficient light emission may not be obtained when the said content is too small. Moreover, when the said content is too much, it is because the film-forming of a light emitting layer may become difficult.

As a method for synthesizing quantum dots, Japanese Patent Publication No. 2005-522005, Japanese Patent Publication No. 2006-520077, Japanese Patent Publication No. 2007-21670 and the like can be referred to.

It is also possible to replace the ligand attached to the surface of the quantum dots with another ligand. For example, TOPO etc. can be substituted with a silane coupling agent by mixing the quantum dot which TOPO etc. adhered to the surface with a large amount of silane coupling agents. It is preferable to make the temperature at the time of replacing a ligand about room temperature.

Moreover, about Unexamined-Japanese-Patent No. 2007-21670 etc. about the substitution method of a ligand can be referred.

As a commercial item of a quantum dot with a ligand such as TOPO, a fluorescent semiconductor nanocrystal " Ebidot " manufactured by Evidence Technology Co., Ltd. can be used.

(Religioner)

As a ligand used for this aspect, what is generally used as a ligand of a quantum dot can be used. For example, alkyl phosphines such as tri-n-octylphosphine (TOP), alkyl phosphine oxides such as tri-n-octylphosphine oxide (TOPO), alkyl phosphonic acid, tris-hydroxypropyl phosphine (tHPP) Alkylphosphinic acid, pyridine, furan, hexadecylamine, etc., etc. are mentioned.

In addition, in this aspect, a silane coupling agent can be used as a ligand. In this case, the quantum dot and the silane coupling agent are coordinately bonded. When the quantum dots are compound semiconductors, since the surface of the inorganic material is generally lyophilic, the -OH group of the Si-OH group of the hydrolyzed silane coupling agent can be coordinated with the quantum dots.

As a ligand, a silane coupling agent is preferable among the above. A light emitting layer can be hardened by using the coating liquid for light emitting layer formation containing a silane coupling agent. This is because the stability of the quantum dots in the light emitting layer can be improved and the lifespan characteristics can be improved. Furthermore, the thermal stability (Tg: glass transition temperature) of a light emitting layer can also be improved. In addition, since the silane coupling agent is relatively easy in molecular design, the life characteristics can be improved by using a silane coupling agent having a functional group exhibiting various functionalities.

In addition, when the wettability changing layer contains organopolysiloxane, the adhesion between the first electrode layer, the wettability changing layer and the light emitting layer can be improved by using a silane coupling agent as a ligand.

When the light emitting layer is cured, the light emitting layer is not dissolved in the solvent in the coating liquid for forming the hole injection transport layer or the electron injection transport layer when the hole injection transport layer or the electron injection transport layer is formed using the coating solution on the light emitting layer. Instead, the hole injection transport layer, the electron injection transport layer, or the like can be stably laminated on the light emitting layer.

The silane coupling agent used in the present embodiment is not particularly limited as long as it can coordinate with quantum dots and stabilize the quantum dots. Examples of the silane coupling agent include (2) reactive silicones such as (1) chloro or alkoxysilane. .

As chloro or alkoxysilane of said (1), it is a following general formula

YnSiX (4-n)

(Wherein Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, X represents an alkoxyl group, an acetyl group or a halogen and n is an integer of 0 to 3)

The silicon compound represented by is used preferably. This silicon compound may be used individually by 1 type, and may use 2 or more types together.

In the silicon compound represented by the above formula, X is a coordinating moiety that coordinates to the terminal and quantum dots. In addition, the terminal portion is a portion where a condensation reaction occurs, and is a portion that bonds between quantum dots in which a silane coupling agent is disposed, insolubilizes the light emitting layer, or contributes to improving adhesion between the light emitting layer and the wettability changing layer.

It is preferable that the alkoxyl group represented by X is a methoxy group, an ethoxy group, a propoxy group, butoxy group.

In the silicon compound represented by the above formula, Y is a functional moiety.

For example, when Y is an alkyl group, it becomes a spacer between quantum dots and becomes a site | part which contributes to solubility. When Y is a fluoroalkyl group, it becomes a spacer between quantum dots and becomes a site | part which shows liquid repellency. When Y is a vinyl group, it becomes a spacer between quantum dots and becomes a site | part which shows (pi) conjugated system. When Y is an amino group, it becomes a spacer between quantum dots and becomes a site | part which shows lyophilic property. When Y is a phenyl group, it becomes a spacer between quantum dots and becomes a site | part which shows water repellency. When Y is an epoxy group, it becomes a spacer between quantum dots and becomes a site | part which contributes to sclerosis | hardenability.

It is preferable that carbon number of group represented by Y exists in the range of 1-20.

As a silicon compound represented by the said chemical formula, the thing specifically described in Unexamined-Japanese-Patent No. 2000-249821 can be used.

In addition, as chloro or alkoxysilane of said (1), it is a following general formula.

YnSiX (4-n)

(Wherein Y is a functional group which shows hole transportability directly bonded through a vinyl group or a phenyl group, a functional group which shows electron transport property bonded through a direct vinyl or phenyl group, or a hole transporting and electron transporting property bonded through a direct, vinyl or phenyl group Represents a functional group capable of representing all, X represents an alkoxyl group, an acetyl group or a halogen, n is an integer from 0 to 3)

The silicon compound represented by is also used preferably. This silicon compound may be used individually by 1 type, and may use 2 or more types together.

In the silicon compound represented by the above formula, X is a coordinating moiety that coordinates to the terminal and quantum dots. In addition, the terminal portion is a portion where a condensation reaction occurs, and is a portion that bonds between quantum dots in which a silane coupling agent is disposed, insolubilizes the light emitting layer, or contributes to improving adhesion between the light emitting layer and the wettability changing layer.

It is preferable that the alkoxyl group represented by X is a methoxy group, an ethoxy group, a propoxy group, butoxy group.

In the silicon compound represented by the above formula, Y is a functional moiety.

For example, when Y is a functional group exhibiting hole transportability bonded directly via a vinyl group or a phenyl group, it becomes a spacer between quantum dots to become a site showing hole transportability. When Y is a functional group exhibiting electron transportability directly bonded via a vinyl group or a phenyl group, it becomes a spacer between quantum dots to become a site showing electron transportability. When Y is a functional group capable of exhibiting both hole transportability and electron transportability bonded directly through a vinyl group or a phenyl group, it becomes a spacer between both dots to become a site capable of exhibiting both hole transportability and electron transportability.

When Y is a functional group which shows the hole transport property couple | bonded directly through the vinyl group or the phenyl group, it is preferable that it is a functional group which shows the hole transport property couple | bonded through the vinyl group or the phenyl group especially. It is because a vinyl group and a phenyl group are site | parts which show (pi) conjugated system.

As a functional group which shows hole transportability, the aromatic amine group containing one or more N atoms, the substituted or unsubstituted C6-C16 aryl group is mentioned, for example.

As an aromatic amine group containing one or more N atoms, an aromatic tertiary amine group containing one or more N atoms is preferable. Specifically N, N'-bis (naphthalen-1-yl) -N, N'-bis (phenyl) -benzidine (α-NPD) or 4,4,4-tris (3-methylphenylphenylamino) tri Triphenylamine, such as phenylamine (MTDATA), is mentioned. As triphenylamine, what has a structure represented by a following formula is mentioned.

Examples of the aryl group having 6 to 16 carbon atoms include a phenyl group, naphthyl group, tolyl group, xylyl group, anthryl group, phenanthryl group, biphenyl group, naphthacenyl group, pentaxenyl group, and the like.

When Y is a functional group which shows the electron transport property couple | bonded directly through the vinyl group or the phenyl group, it is preferable that it is a functional group which shows the electron transport property couple | bonded via the vinyl group or the phenyl group. It is because a vinyl group and a phenyl group are site | parts which show (pi) conjugated system.

As a functional group which shows electron transport property, phenanthroline, a triazole, oxadiazole, aluminum quinolinol, etc. are mentioned, for example. Specifically, vasocuproin (BCP), vasophenanthroline (Bpehn), tris (8-hydroxyquinolinorate) aluminum (Alq3), etc. are mentioned. Examples of oxadiazole and triazole include those having a structure represented by the following chemical formula.

Moreover, as a functional group which shows electron transport property, a substituted or unsubstituted C6-C16 aryl group is illustrated. In addition, the C6-C16 aryl group is the same as the above.

When Y is a functional group capable of exhibiting both hole transportability and electron transportability bonded directly through a vinyl group or a phenyl group, it is preferable that it is a functional group capable of exhibiting both hole transportability and electron transportability bound through a vinyl group or a phenyl group. It is because a vinyl group and a phenyl group are site | parts which show (pi) conjugated system.

Examples of the functional group capable of exhibiting both hole transporting properties and electron transporting properties include distyryl arene, polyaromatics, aromatic condensed rings, carbazoles, heterocycles, and the like. Specifically, the ratio of 4,4'-bis (2,2-diphenyl-ethen-1-yl) diphenyl (DPVBi) and 4,4'-bis (carbazol-9-yl) represented by the following chemical formula Phenyl (CBP), 4,4 ''-di (N-carbazolyl) -2 ', 3', 5 ', 6'-tetraphenyl-p-terphenyl (CzTT), 1,3-bis (carr) Bazol-9-yl) -benzene (m-CP), 9,10- di (naphtha-2-yl) anthracene (DNA), etc. are mentioned.

Moreover, what has a structure represented by a following formula is mentioned.

Moreover, as a functional group which can exhibit both a hole transport property and an electron transport property, a substituted or unsubstituted C6-C16 aryl group is illustrated. In addition, the C6-C16 aryl group is the same as the above.

Moreover, as reactive silicone of said (2), the compound which has frame | skeleton represented by a following formula is mentioned.

Provided that n is an integer of 2 or more, and R ¹ and R ² each represent a substituted or unsubstituted alkyl, alkenyl, aryl or cyanoalkyl group having 1 to 10 carbon atoms, with 40% or less of the total being vinyl or phenyl by molar ratio. Phenyl halide. Moreover, it is preferable that R <^1> , R <^2> is a methyl group, and it is more preferable that a methyl group is 60% or more by molar ratio. The chain terminal or side chain has a reactive group such as at least one or more hydroxyl groups in the molecular chain.

The silane coupling agent may also have charge transport properties. In order to be a silane coupling agent having charge transport properties, electrons in which Y in the above formula in the case of (1) is bonded via a functional group, a direct group, a vinyl group, or a phenyl group, which exhibits hole transporting property directly bonded via a vinyl group or a phenyl group It can be set as a functional group which can exhibit both the hole transporting property and the electron transporting property couple | bonded through the vinyl group or the phenyl group directly, or the functional group which shows transportability.

Moreover, the coating liquid for light emitting layer formation may contain the stable organo silicone compound which does not crosslinking reaction like dimethylpolysiloxane.

(menstruum)

As a solvent which can be used for the coating liquid for light emitting layer formation used for this aspect, if it mixes with the quantum dot in which a ligand was arrange | positioned above, it will not specifically limit. In the case where the ligand is a silane coupling agent, it is preferable not to have turbidity or other effects among them. Examples of such a solvent include aromatic hydrocarbon solvents such as xylene, toluene, cyclohexylbenzene, dihydrobenzofuran, trimethylbenzene, tetramethylbenzene, pyridine, pyrazine, furan, pyrrole, thiophene, methylpyrrolidone, and the like. And aliphatic hydrocarbon solvents such as aromatic heterocyclic compound solvents, hexane, pentane, heptane, and cyclohexane. These solvents may be used alone or in combination.

(Etc)

Various additives can be added to the coating liquid for light emitting layer formation used for this aspect. For example, when forming a light emitting layer by the inkjet method, surfactant etc. can also be added in order to improve discharge property.

In addition, in this aspect, when forming the light emitting layer of three primary colors of red, green, and blue, for example, the coating liquid for forming each color light emitting layer of red, green, and blue is used. As described above, since the quantum dots exhibit different emission spectra depending on the particle diameter, the particle diameter of the quantum dots is adjusted according to each color.

(ii) Formation method of light emitting layer

In this aspect, the light emitting layer forming coating liquid is coated on the lyophilic region to form a light emitting layer.

As a coating method of the coating liquid for light emitting layer formation, for example, a spin coating method, the casting method, the dip coating method, the bar coating method, the blade coating method, the roll coating method, the spray coating method, the flexographic printing method, the gravure printing method, the offset method A printing method, a screen printing method, or the discharge method using a dispenser or an inkjet, etc. are mentioned. Among these, the ejection method, the flexographic printing method, and the gravure printing method are preferably used. In particular, the ejection method is preferable, and furthermore, the inkjet method is preferable. This is because a high-precision pattern can be formed by using the wettability change pattern in this method.

After application of the coating solution for forming the light emitting layer, the coating film may be dried. As a drying method, if it is a method which can form a uniform light emitting layer, it will not specifically limit, For example, a hotplate, an infrared heater, oven, etc. can be used.

Especially, when a ligand is a silane coupling agent, it is preferable to harden | cure after application | coating of the coating liquid for light emitting layer formation. By performing said drying, condensation reaction of a hydrolyzed silane coupling agent advances and a light emitting layer hardens.

The thickness of the light emitting layer is not particularly limited as long as it can provide a function of emitting light by providing a recombination site of electrons and holes, and may be, for example, about 1 nm to 500 nm.

(2) Fourth aspect

The light emitting layer formation process in this aspect apply | coats the coating liquid for light emitting layer formation containing any one or more of a quantum dot with a ligand arrange | positioned around it, and a hole transport material and an electron transport material on the said lyophilic region, It is a process of forming a light emitting layer.

In this embodiment, the light emitting layer can be provided with not only a light emitting function but also a hole transporting function and an electron transporting function. Thereby, the manufacturing process of the EL element can be simplified, and the energy transfer of excitons generated by charge transport to the light emitting layer and recombination of holes and electrons can be efficiently performed, and the lifespan characteristics can be improved. have.

In addition, since the formation method of a light emitting layer is the same as that of the said 3rd aspect, description here is abbreviate | omitted. Hereinafter, the coating liquid for light emitting layer formation is demonstrated.

(i) Coating solution for forming light emitting layer

The coating liquid for light emitting layer formation used for this aspect contains a quantum dot with a ligand arrange | positioned around it, and contains at least any one or more of a hole transport material and an electron carrying material, Usually, , At least one or more of a hole transport material and an electron transport material are dispersed or dissolved in a solvent.

The coating liquid for forming the light emitting layer may contain at least one of a quantum dot having a ligand disposed around the hole, a hole transporting material and an electron transporting material, among others, a quantum dot having a ligand disposed around the hole, and a hole transporting material And it is preferable to contain an electron carrying material. This is because the energy transfer of excitons generated by charge transport to quantum dots and recombination of holes and electrons can be efficiently performed.

In addition, about a ligand, since it is the same as that described in the said 3rd aspect, description here is abbreviate | omitted. Hereinafter, the other structure of the coating liquid for light emitting layer formation is demonstrated.

(Quantum dot)

As content in the coating liquid for light emitting layer formation of the quantum dot arrange | positioned around a ligand, when the total solid in the coating liquid for light emitting layer forming is 100 mass%, it is preferable to exist in the range of 10 mass%-90 mass%, and especially 30 It is preferable to exist in the range of mass%-70 mass%. It is because there exists a possibility that sufficient light emission may not be obtained when the said content is too small. If the content is too large, it is difficult to form the light emitting layer, or it may be difficult to provide a hole transporting function, an electron transporting function, or the like to the light emitting layer.

In addition, about the other point of a quantum dot, since it is the same as that described in the said 3rd aspect, description here is abbreviate | omitted.

(Hole transport material)

As a hole transport material used for this aspect, an arylamine derivative, anthracene derivative, a carbazole derivative, a thiophene derivative, a fluorene derivative, a distyrylbenzene derivative, a spiro compound, etc. are mentioned, for example. Specifically 4,4'-bis [N- (1-naphthyl) -N-phenyl-amino] -biphenyl (α-NPD), N, N'-bis- (3-methylphenyl) -N, N '-Bis- (phenyl) -benzidine (TPD), 4,4', 4 ''-tris [N- (3-methylphenyl) -N-phenyl-amino] -triphenylamine (MTDATA), 9,10- Di-2-naphthylanthracene (DNA), 4,4-N, N'-dicarbazole-biphenyl (CBP), 1,4-bis (2,2-diphenylvinyl) benzene (DPVBi), and the like. Can be mentioned. These materials may be used independently and may use 2 or more types together.

When the coating solution for forming the light emitting layer contains a quantum dot having a ligand disposed around it and a hole transporting material, the mixing ratio of the quantum dot having a ligand disposed around it and the hole transporting material is (quantum dot having a ligand disposed around): (Hole transport material) It is preferable that it is about 1: 0.1-2. This is because if the mixing ratio of the quantum dots is too small, sufficient light emission may not be obtained. If the mixing ratio of the quantum dots is too large, it is difficult to form the light emitting layer, or it may be difficult to give the hole transporting function to the light emitting layer.

(Electronic transport material)

Examples of the electron transporting material used in this embodiment include phenanthroline derivatives such as vasocuproin (BCP) and vasophenanthroline (Bpehn), triazole derivatives, oxadiazole derivatives, and tris (8-quinoli). Aluminum quinolinol complexes, such as knol) aluminum complex (Alq3), etc. are mentioned.

When the coating solution for forming the light emitting layer contains a quantum dot having an ligand disposed around it and an electron transporting material, the mixing ratio of the quantum dot having a ligand disposed around it and the electron transporting material is (quantum dot having a ligand disposed around): (Electronic transport material) It is preferable that it is about 1: 0.1-2. This is because if the mixing ratio of the quantum dots is too small, sufficient light emission may not be obtained. If the mixing ratio of the quantum dots is too large, it is difficult to form the light emitting layer, or it may be difficult to impart an electron transport function to the light emitting layer.

In addition, when the coating liquid for light emitting layer formation contains the quantum dot in which a ligand was arrange | positioned, a hole transport material, and an electron transport material, the mixing ratio of the quantum dot, a hole transport material, and an electron transport material with a ligand arrange | positioned around it is ( Quantum dots with ligands arranged around them: (hole transporting material): (electron transporting material) = 1: 0.1 to 2: It is preferable that it is about 0.1 to 2. This is because if the mixing ratio of the quantum dots is too small, sufficient light emission may not be obtained. If the mixing ratio of the quantum dots is too large, film formation of the light emitting layer may be difficult, or it may be difficult to give a hole transport function or an electron transport function to the light emitting layer.

(menstruum)

As a solvent which can be used for the coating liquid for light emitting layer formation used for this aspect, a nonpolar solvent is preferable, For example, aromatic hydrocarbon solvent, such as xylene, toluene, cyclohexylbenzene, dihydrobenzofuran, trimethylbenzene, tetramethylbenzene, etc. And aromatic heterocyclic compound solvents such as pyridine, pyrazine, furan, pyrrole, thiophene and methylpyrrolidone, and aliphatic hydrocarbon solvents such as hexane, pentane, heptane and cyclohexane. These solvents may be used alone or in combination.

(Etc)

The coating liquid for light emitting layer formation can be manufactured by first dissolving at least one or more of a hole transport material and an electron transport material in a solvent, and disperse | distributing the quantum dot by which the ligand was arrange | positioned in this solution.

In addition, about another point of the coating liquid for light emitting layer formation, it is the same as that of the said 3rd aspect.

In addition, the light emitting layer formed in the light emitting layer formation process of this aspect is described in detail in Unexamined-Japanese-Patent No. 2005-522005.

(3) Fifth aspect

The light emitting layer formation process in this aspect forms the coating film by apply | coating the said light emitting layer formation coating liquid using the said light emitting layer formation coating liquid containing the quantum dot which has a ligand arrange | positioned around this, a hole transport material, and a solvent. Thereafter, while removing the solvent in the coating film, the hole transporting material is separated to the first electrode layer side, and a quantum dot having a ligand arranged around the separation is separated to the outermost surface side of the coating film so that the hole transporting layer and the light emitting layer are collectively. It is a process of forming.

In this embodiment, a coating solution for forming a light emitting layer containing a quantum dot having a ligand disposed around it, a hole transporting material and a solvent is applied onto a substrate on which a photoresist layer is formed in a pattern, and a quantum dot having a ligand arranged around By phase-separating (vertical phase-separating) a hole transport material, the hole transport layer 9 and the light emitting layer 7 can be collectively formed as shown in FIG. In this case, the hole transport layer 9 and the light emitting layer 7 are phase separated, and the phase separation interface 23 is provided between the hole transport layer 9 and the light emitting layer 7.

In the case of having a phase separation interface between the hole transport layer and the light emitting layer, the phase separation interface 23 is macroscopically parallel to the surface of the first electrode layer 2 as illustrated in FIG. 3, and microscopically as illustrated in FIG. 4. As a result, the light emitting layer 7 and the hole transporting layer 9 are in a state where the concave-convex shape (overlapped) enters each other. As a result, the contact area between the hole transporting layer and the light emitting layer is increased, and the recombination site of electrons and holes is expanded. In addition, since this recombination site exists in the part which deviates from the 1st electrode layer, the place which emits light as a result expands (the number of molecules which contribute to light emission increases). For this reason, the luminous efficiency can be improved and the lifespan can be further extended.

In addition, since the interface between the hole transporting layer and the light emitting layer is not uniform (flat) and is uneven, it prevents the holes and electrons from being excited and combined at the same time even if the driving voltage is increased, thereby preventing the intensity of light emission from rapidly increasing. Can be. Therefore, since the luminance can be increased slowly in accordance with the driving voltage amount, the control of the light emission luminance and the low luminance gradation control can be easily performed. In addition, there is an advantage that a complicated peripheral circuit for finely controlling the driving voltage is unnecessary.

Hereinafter, the coating liquid for light emitting layer formation and the formation method of a light emitting layer are demonstrated.

(i) Coating solution for forming light emitting layer

The coating liquid for light emitting layer formation used for this aspect contains a quantum dot, a hole transport material, and a solvent with a ligand arrange | positioned around it.

In addition, since it is the same as that described in the said 3rd aspect about a quantum dot and a ligand, and it is the same as that described in the said 4th aspect about a hole transport material and a solvent, description here is abbreviate | omitted.

In this embodiment, as content in the coating liquid for light emitting layer formation of the quantum dot arrange | positioned at the circumference | surroundings, when the total solid in the coating liquid for light emitting layer formation is 100 mass%, it is preferable to exist in the range of 10 mass%-90 mass%. Among these, it is preferable to exist in the range of 30 mass%-70 mass%. It is because there exists a possibility that sufficient light emission may not be obtained when the said content is too small. If the content is too large, it is difficult to phase separate the quantum dot and the hole transport material in which the ligand is disposed around.

In addition, it is preferable that the mixing ratio of the quantum dot in which a ligand is arrange | positioned around a hole in a coating liquid for light emitting layer formation, and a hole transport material is (quantum dot in which a ligand is arrange | positioned around): (hole transport material) = 1: 0.1-2 or so Do. This is because if the mixing ratio of the quantum dots is too small, sufficient light emission may not be obtained. If the mixing ratio of the quantum dots is too large, it is difficult to phase separate the quantum dots and the hole transporting material.

The coating liquid for light emitting layer formation used for this aspect can be manufactured by melt | dissolving a positive hole transport material first in a solvent, and disperse | distributing the quantum dot by which the ligand was arrange | positioned in this solution.

In addition, about another point of the coating liquid for light emitting layer formation, it is the same as that of the said 3rd aspect.

(ii) Formation method of light emitting layer

In this aspect, after forming the coating film by apply | coating the said coating solution for light emitting layer formation on the said lyophilic area | region, a ligand is arrange | positioned around the said hole transport material to the said 1st electrode layer, removing the said solvent in the said coating film. The quantum dots are separated to the outermost surface side of the coating film to form the hole transporting layer and the light emitting layer collectively.

In addition, since it is the same as that of the said 3rd aspect, the application method of the coating liquid for light emitting layer formation is abbreviate | omitted here.

After apply | coating the said coating liquid for light emitting layer formation and forming a coating film, a solvent is removed from the coating film. When the solvent is removed, in the coating film, as illustrated in FIG. 4, a quantum dot 22 having a hole carrier material (not shown) is disposed on the first electrode layer 2 side and a ligand (not shown) is arranged around the coating film. It separates in the up-down direction to the outermost surface side, and the coating film is solidified. In this way, the hole transporting layer 9 and the light emitting layer 7 are collectively formed. That is, the hole transport layer and the light emitting layer are collectively formed by phase separation.

At this time, the type of solvent, the weight average molecular weight of the hole transport material, the content of the hole transport material in the coating liquid for forming the light emitting layer, the content of the quantum dots and the ligand in the coating liquid for forming the light emitting layer, the speed of removing the solvent, and the removal of the solvent Can be controlled by appropriately setting one or more conditions among the atmosphere, the surface state of the base layer to which the coating liquid for forming the light emitting layer is applied, and the like. .

For example, the atmosphere at the time of removing a solvent can be made into the atmosphere containing the vapor of a polar solvent. As a result, the quantum dots in which the ligands are arranged can be more reliably concentrated on the upper side in the coating film. As this polar solvent, water, alcohol, such as methanol, ethanol, isopropanol, etc. are mentioned, for example.

Moreover, you may dry a coating film after application | coating of the coating liquid for light emitting layer formation. In addition, about a drying method, since it is the same as that of the said 3rd aspect, description here is abbreviate | omitted.

Especially, when a ligand is a silane coupling agent, it is preferable to harden a coating film after application | coating of the coating liquid for light emitting layer formation. By performing said drying, condensation reaction of a hydrolyzed silane coupling agent advances and a light emitting layer hardens.

The thickness of the light emitting layer is not particularly limited as long as it can provide a function of emitting light by providing a recombination site of electrons and holes, and may be, for example, about 1 nm to 500 nm.

4. Hole injection transport layer formation process

In the present embodiment, a hole injection transport layer forming step of forming a hole injection transport layer on the lyophilic region may be performed before the light emitting layer formation step. By providing the hole injection transport layer, the injection of holes into the light emitting layer is stabilized or the transport of holes is smoothed, so that the luminous efficiency can be increased.

In the case of performing the hole injection transport layer formation step and the light emitting layer formation step, the hole injection transport layer is first formed only on the lyophilic region. Since the surface of the hole injection transport layer is lyophilic and the region in which the hole injection transport layer is not formed is a liquid repellent region, the light emitting layer can be formed only on the lyophilic region due to this wettability difference.

The hole injection transport layer may be a hole injection layer having a hole injection function for stably injecting holes injected from the anode into the light emitting layer, or may be a hole transport layer having a hole transport function for transporting holes injected from the anode into the light emitting layer, The injection layer and the hole transport layer may be laminated, or may be a single layer having both a hole injection function and a hole transport function.

In the light emitting layer forming step, when a single light emitting layer is formed by using a light emitting layer forming coating solution containing a quantum dot and a hole transporting material having a ligand disposed around it, or when the hole transporting layer and the light emitting layer are collectively formed. In this step, it is preferable to form a hole injection layer as the hole injection transport layer.

The hole injection material used in the hole injection layer is not particularly limited as long as it can stabilize the injection of holes into the light emitting layer, and examples thereof include phenylamines, starburst amines, phthalocyanines, vanadium oxide, molybdenum oxide, and oxides. Oxides such as ruthenium and aluminum oxide, amorphous carbon, polyaniline, polythiophene, polyphenylenevinylene and conductive polymers such as these derivatives. The conductive polymer may be doped with an acid. Specifically 4,4'-bis [N- (1-naphthyl) -N-phenyl-amino] -biphenyl (α-NPD), 4,4 ', 4' '-tris (N, N-di Phenyl-amino) -triphenylamine (TDATA), 4,4 ', 4' '-tris [N- (3-methylphenyl) -N-phenyl-amino] -triphenylamine (MTDATA), polyvinylcarbazole, Poly (3,4-ethylenedioxythiophene) / polystyrenesulfonic acid (PEDOT / PSS) and the like. These materials may be used independently and may use 2 or more types together.

The film thickness of the hole injection layer is not particularly limited as long as its function is sufficiently exhibited. Specifically, the thickness is preferably in the range of 5 nm to 200 nm, and more preferably in the range of 10 nm to 100 nm.

The hole transporting material used for the hole transporting layer is not particularly limited as long as it is a material capable of stably transporting holes injected from the anode into the light emitting layer, and for example, the holes described in the section "3. Light emitting layer forming process". Transport materials can be used.

The film thickness of the hole transport layer is not particularly limited as long as the function is sufficiently exhibited, but it is preferably in the range of 5 nm to 200 nm, more preferably in the range of 10 nm to 100 nm.

In this step, the hole injection transport layer may be formed so as to be insoluble in the solvent of the coating liquid for forming the light emitting layer. Accordingly, when the light emitting layer is formed on the hole injection transport layer, the hole injection transport layer is not dissolved even when the solvent of the light emitting layer forming coating liquid contacts the hole injection transport layer, so that the light emitting layer can be laminated stably. Furthermore, the fall of the characteristic of a hole injection transport layer can be suppressed.

In order to make a hole injection transport layer insoluble with respect to the solvent of the coating liquid for light emitting layer formation, a photoinitiator etc. can be contained in a hole injection transport layer. For example, by mixing the photoinitiator and the like described in the Applied physics letter, Vol 81, (2002) with a conductive polymer, it can be cured by ultraviolet irradiation.

Especially, in order to make a hole injection transport layer insoluble with respect to the solvent of the coating liquid for light emitting layer formation, it is preferable to use the material which changes solubility by the action of a curable binder or thermal energy or radiation to a hole injection transport layer. That is, it is preferable that the coating liquid for hole injection transport layer formation contains a hole injection material, a hole transport material, etc., or a curable binder, or a material whose solubility is changed by the action of thermal energy or radiation.

In particular, it is preferable to apply | coat and harden the coating liquid for hole injection transport layer formation containing a hole injection material, a hole transport material, etc., and a curable binder, and to form a hole injection transport layer.

Hereinafter, when the coating liquid for hole injection transport layer formation containing a hardening binder etc. with a hole injection material, a hole transport material, etc. is apply | coated and hardened | cured to form a hole injection transport layer (6th aspect), by the action of thermal energy or a radiation The coating solution for forming a hole injection transport layer containing a material whose solubility is changed is described, which is divided into the case where the hole injection transport layer is formed by applying thermal energy or irradiating radiation (the seventh embodiment).

(1) Sixth aspect

The hole injection transport layer formation process in this aspect is a process of apply | coating the coating liquid for hole injection transport layer formation containing a hole injection material, a hole transport material, etc., and a curable binder, and hardening | curing to form a hole injection transport layer.

In addition, the hole injection material and the hole transport material are as described above.

In this aspect, it is preferable that a hole injection transport layer formation process is a hole injection layer formation process which apply | coats the coating liquid for hole injection layer formation containing a hole injection material and a curable binder, and hardens to form a hole injection layer.

As a curable binder used for this aspect, what hardens | cures by the action of heat energy or a radiation is preferable, For example, a sol-gel reaction liquid, a photocurable resin, and a thermosetting resin are mentioned. In addition, a sol-gel reaction liquid means the reaction liquid which gelatinizes after hardening.

Among these, it is preferable that a curable binder contains organopolysiloxane. As this organopolysiloxane, the thing described in Unexamined-Japanese-Patent No. 2000-249821, etc. can be used, for example.

The coating liquid for forming a hole injection transport layer is prepared by dispersing or dissolving the hole injection material or the hole transport material and the like in a solvent. For example, when the curable binder contains organopolysiloxane, alcohols such as ethanol and isopropanol are preferably used as the solvent.

As a coating method of the coating liquid for hole injection transport layer formation, a spin coating method, the spray coating method, the dip coating method, the roll coating method, the bead coating method, etc. are mentioned, for example.

After apply | coating the coating liquid for hole injection transport layer formation, it hardens | cures. As a method of hardening, provision of heat energy or irradiation of a radiation is mentioned.

(2) Seventh aspect

In the hole injection transport layer formation step in this embodiment, a coating liquid for hole injection transport layer formation containing a material whose solubility is changed by the action of thermal energy or radiation is applied, and the thermal energy is applied or the radiation is irradiated to inject the hole. It is a process of forming a transport layer.

Here, the change in the solubility of the material means that the polarity of the solvent in which the main component of the material is dissolved or dispersed is changed. When the solubility of the material is changed by applying heat energy or irradiating radiation to the layer containing the material whose solubility is changed by the action of heat energy or radiation, the solvent and the heat energy of the coating liquid for forming a hole injection transport layer are provided. Alternatively, the solvent in which the hole injection transport layer after irradiation is dissolved differs in polarity.

The degree to which the solubility of the material is changed may be such that the hole injection transport layer after applying heat energy or radiation is not substantially dissolved or mixed with the solvent used in the coating liquid for forming the hole injection transport layer. Specifically, the hole injection transport layer after applying heat energy or irradiation may be insoluble in the coating liquid for hole injection transport layer formation.

As a material whose solubility is changed by the action of thermal energy or radiation used in the present embodiment, for example, part or all of the hydrophilic group of the hydrophilic organic material is converted into a lipophilic group, and the lipophilic group is caused by the action of thermal energy or radiation. Part or all of is returned to the hydrophilic group is preferably used.

In the above materials, not all of the hydrophilic groups of the hydrophilic organic material need to be converted to a lipophilic group. As a ratio in which a hydrophilic group is converted into a lipophilic group, it may be the grade which can maintain the solubility more than desired concentration with respect to a general non-aqueous organic solvent. Specifically, the hydrophilic group is converted into a lipophilic group to such an extent that a hydrophilic organic material dissolved or dispersed in water or an alcoholic solvent is dissolved in a mass of 0.5 mass% or more in toluene, xylene, ethyl acetate, cyclohexanone, etc., which are common non-aqueous solvents. It is preferable.

In addition, in the said material, it is not necessary for all lipophilic groups to return to a hydrophilic group. The ratio at which the lipophilic group returns to the hydrophilic group may be such that the hole injection transport layer is not dissolved in the solvent of the coating liquid for forming the light emitting layer. Specifically, it is preferable that the lipophilic group is returned to the hydrophilic group to such an extent that a material dissolved in 0.5% by mass or more of toluene, xylene, ethyl acetate, cyclohexanone, or the like becomes insoluble or poorly soluble in toluene, xylene, ethyl acetate, cyclohexanone, or the like. . At this time, it may not return completely to the original hydrophilic organic material.

The hydrophilic organic material is not particularly limited as long as it has a hydrophilic group, is dispersed or dissolved in water, and exhibits a function required for the hole injection transport layer. When a hole injection transport layer is a hole injection layer, what is described in Unexamined-Japanese-Patent No. 2006-318876, etc. are mentioned, for example.

As a method of converting a hydrophilic group in a hydrophilic organic material to a lipophilic group, since part or all of a lipophilic group returns to a hydrophilic group by the action of heat energy or radiation, it is preferable that it is a method of using a protective reaction. Here, a protection reaction means reaction which derivatizes a hydrophilic group and introduces a protecting group temporarily to a hydrophilic group. As a protective reaction, what is described in Unexamined-Japanese-Patent No. 2006-318876, etc. are mentioned, for example.

The coating liquid for hole injection transport layer formation can be manufactured by disperse | distributing or melt | dissolving the material in which one or all the hydrophilic groups of said hydrophilic organic material were converted into the lipophilic group in a solvent. At this time, as a solvent, what can disperse | distribute or melt | dissolve a lipophilic material is used. As such a solvent, the thing described in Unexamined-Japanese-Patent No. 2006-318876, etc. can be used, for example.

The concentration of the material in which part or all of the hydrophilic groups of the hydrophilic organic material in the coating liquid for forming the hole injection transport layer is converted into a lipophilic group is different depending on the component or composition of the material, but is usually set to 0.1% by mass or more, Preferably it is about 1-5 mass%.

The hole injection transport layer can be formed by applying thermal energy to the coating film obtained by applying the coating liquid for hole injection transport layer formation or by irradiating radiation to change the solubility of the coating film. After application of the coating liquid for hole injection transport layer formation, drying may be performed. The provision of thermal energy and irradiation of radiation can be made, for example, under the conditions described in Japanese Patent Laid-Open No. 2006-318876.

Moreover, the mechanism by which the solubility of a material changes by the action of heat energy or radiation is described in detail in Unexamined-Japanese-Patent No. 2006-318876.

5. Electron injection transport layer formation process

In this embodiment, an electron injection transport layer forming step of forming an electron injection transport layer on the light emitting layer after the light emitting layer forming step may be performed. By providing the electron injection transport layer, the injection of electrons into the light emitting layer is stabilized or the electrons are transported smoothly, so that the luminous efficiency can be increased.

The electron injection transport layer may be an electron injection layer having an electron injection function for stably injecting electrons injected from the cathode into the light emitting layer, or may be an electron transport layer having an electron transport function for transporting electrons injected from the cathode into the light emitting layer, The injection layer and the electron transport layer may be laminated, or may be a single layer having both an electron injection function and an electron transport function.

In the light emitting layer forming step, when a single light emitting layer is formed by using the light emitting layer forming coating solution containing a quantum dot and an electron transporting material having a ligand disposed around it, in this step, the electron injection layer is used as the electron injection transporting layer. It is preferable to form.

The electron injection material used for the electron injection layer is not particularly limited as long as it is a material capable of stabilizing the injection of electrons into the light emitting layer, and for example, alkali metal or alkaline earth such as Ba, Ca, Li, Cs, Mg, Sr, etc. Alkali, such as a single metal, alloys of alkali metals, such as aluminum lithium alloys, alkali metals, such as magnesium oxide and strontium oxide, or oxides of alkaline earth metals, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, lithium fluoride, cesium fluoride Organic complexes of alkali metals, such as fluoride of a metal or alkaline-earth metal, sodium polymethylmethacrylate polystyrene sulfonate, etc. are mentioned. Moreover, like Ca / LiF, it is also possible to laminate | stack and use them.

Although it will not specifically limit, if the film thickness of an electron injection layer is the film thickness in which the function is fully exhibited, It is preferable to exist in the range of 0.1 nm-200 nm specifically, More preferably, it exists in the range of 0.5 nm-100 nm.

The electron transporting material used for the electron transporting layer is not particularly limited as long as it is a material capable of stably transporting electrons injected from the cathode into the light emitting layer. For example, the electron transporting material described in the section "3. Electron transport materials can be used.

Although it will not specifically limit, if the film thickness of an electron carrying layer is the film thickness in which the function is fully exhibited, It is preferable to exist in the range of 1 nm-100 nm specifically, More preferably, it exists in the range of 1 nm-50 nm.

Moreover, the electron transport material doped with alkali metals or alkaline earth metals, such as Li, Cs, Ba, Sr, can be mentioned as a formation material of the single layer which has both the electron injection function and the electron transport function. Examples of the electron transporting material include phenanthroline derivatives such as vasocuproin (BCP) and vasophenanthroline (Bpehn). In addition, the molar ratio of the electron transporting material and the metal to be doped is preferably in the range of 1: 1 to 1: 3, more preferably in the range of 1: 1 to 1: 2. The electron transport material doped with the alkali metal or the alkaline earth metal has a relatively high electron mobility and a high transmittance as compared to the metal alone.

The film thickness of the single layer having both the electron injection function and the electron transport function is not particularly limited as long as the function is sufficiently exhibited, but it is particularly preferably in the range of 0.1 nm to 100 nm, more preferably. It is in the range of 0.1 nm to 50 nm.

As a method of forming an electron injection transport layer, a dry process, such as a vacuum deposition method, may be sufficient, for example, and a wet process, such as a spin coating method, may be sufficient. In the present embodiment, the light emitting layer can be cured by using a silane coupling agent as the ligand, so that even when a wet process is used, the electron injection transport layer can be stably formed on the light emitting layer.

6. Second electrode layer forming process

In the present embodiment, a second electrode layer forming step of forming a second electrode layer on the light emitting layer is usually performed after the light emitting layer step. When the electron injection transport layer forming step is performed, a second electrode layer forming step of forming a second electrode layer on the light emitting layer after the electron injection transport layer forming step is performed.

The second electrode layer may be an electrode facing the first electrode layer, may be an anode, or may be a cathode.

The material for forming the second electrode layer is not particularly limited as long as it is a material having conductivity. For example, when taking out light from the 2nd electrode layer side, it is preferable that a 2nd electrode layer has transparency. On the other hand, in the case where light is taken out from the first electrode layer side, transparency is not required for the second electrode layer. In addition, about the material which has electroconductivity, since it is the same as what was described in the term of the said 1st electrode layer, description here is abbreviate | omitted.

In addition, since the film forming method and patterning method of a 2nd electrode layer are the same as the film forming method and patterning method of a said 1st electrode layer, it abbreviate | omits description here.

7. Insulation Layer Forming Process

In this embodiment, the insulating layer forming process of forming an insulating layer in the opening part of the 1st electrode layer pattern on a board | substrate may be performed before the said wettability change layer forming process. The insulating layer is provided to prevent conduction between adjacent first electrode layer patterns or conduction between the first electrode layer and the second electrode layer. The portion where this insulating layer is formed becomes a non-light emitting region.

The insulating layer is formed in the opening of the pattern of the first electrode layer on the substrate, and is typically formed to cover the end of the pattern of the first electrode layer.

It will not specifically limit, if it has insulating property as a forming material of this insulating layer, For example, photocurable resin, such as photosensitive polyimide resin and acrylic resin, thermosetting resin, an inorganic material, etc. can be used.

Moreover, as a formation method of an insulating layer, general methods, such as the photolithographic method and the printing method, can be used.

8. Other Process

In this embodiment, the process of forming the barrier layer which protects a light emitting layer etc. from the influence of oxygen and water vapor, and the low refractive index layer which improves light extraction efficiency on a 2nd electrode layer can be performed.

II. Second embodiment

A second embodiment of the method for manufacturing an EL device of the present invention includes a wettability changing layer forming step of forming a wettability changing layer whose wettability is changed by the action of a photocatalyst according to energy irradiation on a substrate on which a first electrode layer is formed; After arranging the photocatalyst treatment layer gas on which the photocatalyst treatment layer containing at least a photocatalyst is formed on the substrate with a gap in which the action of the photocatalyst due to energy irradiation can be applied to the wettability varying layer, And a wettability change pattern forming step of forming a wettability change pattern including a lyophilic region and a liquid-repellent region on the surface of the wettability-changing layer by irradiation with energy, and a quantum dot having a ligand disposed around the lyophilic region. It is characterized by having a light emitting layer formation process of apply | coating the light emitting layer forming coating liquid to form a light emitting layer.

The manufacturing method of the EL element of this embodiment is demonstrated, referring drawings.

5 is a flowchart showing an example of a method of manufacturing the EL device of the present embodiment. First, the first electrode layer 2 is formed in a pattern shape on the substrate 1, the insulating layer 3 is formed in the pattern opening of the first electrode layer 2, and the first electrode layer 2 and the insulating layer ( 3) The wettability changing layer 4 is formed on it (FIG. 5 (a), a wettability changing layer formation process).

Subsequently, as illustrated in FIG. 5B, light formed on the base 32 to cover the base 32, the light blocking portion 33 formed in a pattern shape on the base 32, and the light blocking portion 33. A photocatalyst treatment layer substrate (photocatalyst treatment layer gas) 31 having a catalyst treatment layer 34 is prepared. Subsequently, the photocatalyst treatment layer 34 and the wettability change layer 4 of the photocatalyst treatment layer substrate 31 face each other, and the ultraviolet ray 12 is irradiated. As shown in FIG. 5 (c) by the irradiation of the ultraviolet ray 12, the wettability of the wettability changing layer 4 with the liquid in the irradiated portion of the wettability varying layer 4 from the action of the photocatalyst contained in the photocatalytic treatment layer 34. The contact angle is changed to lower. The region whose wettability has changed so that the contact angle with this liquid falls is set to the lyophilic region 5. In the unirradiated portion, the wettability is not changed. The region where this wettability is not changed is referred to as the liquid repellent region 6. In addition, the photocatalyst treatment layer substrate 31 is removed from the wettability changing layer 4. As a result, a wettability change pattern including the lyophilic region 5 and the liquid repellent region 6 is formed on the wettability changing layer 4 surface. 5 (b) and 5 (c) show a wettability change pattern forming process.

Since the wettability change layer 4 is changed in wettability by the action of a photocatalyst by energy irradiation, there is a difference in wettability in the lyophilic region 5 as the irradiated portion and the liquid repellent region 6 as the unirradiated portion.

Subsequently, using this wettability difference, the coating liquid for forming a light emitting layer is applied onto the wettability change pattern including the lyophilic region 5 and the liquid repellent region 6, and the light emitting layer 7 is disposed only on the lyophilic region 5. ) Is formed (Fig. 5 (d), light emitting layer forming step).

The quantum dot 22 in which the ligand 21 was arrange | positioned around the luminescent layer forming coating liquid as shown in FIG. 2 is used. That is, the ligand 21 is affixed to the surface of the quantum dot 22, and the quantum dot 22 with this ligand 21 attached to the surface is used for the coating liquid for light emitting layer formation.

Next, the second electrode layer 8 is formed on the light emitting layer 7 (Fig. 5 (e)). At this time, for example, when the second electrode layer 8 is used as a transparent electrode, an EL element of a top emission type is obtained. When the first electrode layer 2 is used as a transparent electrode, an EL element of a bottom emission type is obtained. .

In this embodiment, the wettability change layer is irradiated with energy through a photocatalyst treatment layer containing a photocatalyst to form a wettability change pattern including a lyophilic region and a liquid repellent region on the surface of the wettability change layer. Further, the light emitting layer is patterned by using the wettability changing pattern formed on the surface of the wettability changing layer. Therefore, it is possible to easily pattern the light emitting layer without the need for complicated patterning process or expensive vacuum equipment.

In the present embodiment, the wettability-modifying layer is pattern-irradiated with energy through the photocatalyst treatment layer containing the photocatalyst, thereby changing the wettability by the action of the photocatalyst with respect to the wettability-modifying layer containing no photocatalyst. Can be. In addition, after the wettability change pattern is formed on the wettability change layer surface, the photocatalyst treatment layer substrate having the photocatalytic treatment layer is removed from the wettability change layer, so that the photocatalyst is not included in the EL element itself. In other words, the photocatalyst is included in the photocatalyst treatment layer and is not included in the wettability changing layer. Therefore, the smoothness of the wettability varying layer can be improved, and the barrier at the interface between the wettability varying layer and the light emitting layer can be reduced. Thereby, it is possible to improve the light emission characteristics such as reducing the driving voltage and increasing luminance and luminous efficiency. It is also possible to prevent a short circuit between the electrodes.

In addition, in this embodiment, it is preferable that the ligand adhering to the surface of a quantum dot is a silane coupling agent. Thereby, a light emitting layer can be made hard, the stability of the quantum dot in a light emitting layer can be made favorable, and a lifetime characteristic can be improved. In addition, since the silane coupling agent is relatively easy in molecular design, it is possible to improve the life characteristics by using a silane coupling agent having a functional group exhibiting various functionalities.

In addition, the wettability changing layer preferably contains an organopolysiloxane. In this case, the organopolysiloxane in the wettability changing layer is bonded to the first electrode layer, and the silane coupling agent in the light emitting layer is bonded to the wettability changing layer, whereby the adhesion between the first electrode layer, the wettability changing layer and the light emitting layer can be improved. Thereby, it is possible to prevent the fall of the life characteristic by the interlayer peeling etc. at the time of EL element drive etc.

In addition, about the light emitting layer formation process, since it is the same as that of the said 1st Embodiment, description here is abbreviate | omitted. Hereinafter, another process in the manufacturing method of an EL element is demonstrated.

1. Wetability change layer forming process

The wettability changing layer forming process in this embodiment is a process of forming the wettability changing layer whose wettability changes by the action of the photocatalyst by energy irradiation on the board | substrate with which the 1st electrode layer was formed.

The wettability changing layer used in the present embodiment is inert to energy. Here, energy means energy irradiated when a photocatalyst is made to act, and an ultraviolet-ray etc. are mentioned specifically ,. In addition, that a wettability change layer is inert with respect to energy means that when the ultraviolet-ray etc. irradiate a wettability change layer, the constituent material of a wettability change layer does not perform any reaction.

As described above, the wettability changing layer in the present embodiment is capable of reacting by the action of a photocatalyst, and does not react even if energy is irradiated without the presence of the photocatalyst. That is, that the wettability changing layer is inert to energy specifically means that the wettability changing layer is substantially free of a photocatalyst.

In addition, that a wettability change layer does not contain a photocatalyst substantially means that content of the photocatalyst in a wettability change layer is 1 weight% or less.

Thus, since the wettability change layer in this embodiment does not contain a photocatalyst substantially, smoothness is favorable and the barrier at the interface of a wettability change layer and a light emitting layer can be reduced. Thereby, it is possible to improve the light emission characteristics such as reducing the driving voltage and increasing luminance and luminous efficiency. It is also possible to prevent a short circuit between the electrodes.

The wettability changing layer is not particularly limited as long as the wettability is changed by the action of a photocatalyst according to energy irradiation. The material used for the wettability-changing layer is not particularly limited as long as it is a material whose wettability is changed by the action of the photocatalyst due to energy irradiation, and has a main chain that is hardly deteriorated or decomposed by the action of the photocatalyst. As a material used for such a wettability change layer, (1) organopolysiloxane which hydrolyzes and polycondenses chloro or alkoxysilane etc. by a sol-gel reaction etc. and exhibits great strength, (2) reactivity excellent in water repellency and oil repellency Organopolysiloxanes, such as organopolysiloxane which bridge | crosslinked silicone, are mentioned.

In addition, since it is the same as that of what was described in the said 1st Embodiment about organopolysiloxane, description here is abbreviate | omitted.

It is also possible to mix with the organopolysiloxane described above a stable organosilicon compound which does not undergo a crosslinking reaction such as dimethylpolysiloxane.

Thus, although various materials, such as organopolysiloxane, can be used for a wettability change layer, it is preferable that a wettability change layer contains fluorine especially.

In addition, about the case where a wettability change layer contains fluorine, since it described in the said 1st Embodiment, the description here is abbreviate | omitted.

In addition, the wettability changing layer may contain, in addition to the above-mentioned materials, for example, the same surfactants, additives and the like as described in JP-A-2000-249821.

In addition, since the formation method, film thickness, etc. of a wettability change layer are the same as that of what was described in the said 1st Embodiment, the description here is abbreviate | omitted.

2. Wetability change pattern forming process

In the wettability change pattern forming step of the present embodiment, a photocatalyst treatment layer substrate on which a photocatalyst treatment layer containing at least a photocatalyst is formed on a substrate is formed by the action of the photocatalyst according to energy irradiation on the wettability variation layer. After arrange | positioning the space | interval which may exist, it is a process of forming a wettability change pattern containing a lyophilic region and a liquid repellent region on the surface of the said wettability change layer by energy irradiation in a pattern shape.

Hereinafter, the arrangement of the photocatalyst treatment layer substrate, the photocatalyst treatment layer substrate, and the wettability change layer, the energy irradiation, and the wettability change pattern will be described.

(1) Photocatalyst Treatment Layer Substrate (Photocatalyst Treatment Layer Gas)

In the present embodiment, when the wettability change pattern is formed on the surface of the wettability change layer whose wettability is changed by the action of the photocatalyst due to energy irradiation, the photocatalyst is contained in order to cause the action of the photocatalyst on the wettability change layer. A photocatalyst treatment layer substrate having a photocatalyst treatment layer is used. By placing the photocatalyst treatment layer substrate at a predetermined gap with respect to the wettability varying layer and irradiating energy in a pattern, the wettability change pattern can be formed on the surface of the wettability varying layer.

The photocatalyst treatment layer substrate used in the present embodiment has a substrate and a photocatalyst treatment layer formed on the substrate. In addition, a light shielding portion may be formed in a pattern on the photocatalyst treatment layer substrate. Hereinafter, a photocatalyst treatment layer, a base | substrate, and a light shielding part are demonstrated.

(i) photocatalyst treatment layer

The photocatalyst treatment layer used for this embodiment contains a photocatalyst. As a photocatalyst treatment layer, if a photocatalyst in a photocatalyst treatment layer is a structure which changes the wettability of the surface of a wettability change layer, it will not specifically limit. The photocatalyst treatment layer may be composed of, for example, a photocatalyst and a binder, or may be composed of a photocatalyst alone. In the case of the photocatalyst treatment layer containing only a photocatalyst, since the efficiency with respect to the change of the wettability of the surface of a wettability change layer improves, it is advantageous in terms of cost, such as shortening of processing time. Moreover, in the case of the photocatalyst treatment layer containing a photocatalyst and a binder, it has the advantage that formation of a photocatalyst treatment layer is easy.

In addition, about a photocatalyst, since it is the same as that of what was described in the term of the wettability change layer of said 1st Embodiment, the description here is abbreviate | omitted.

In addition, when the photocatalyst treatment layer contains a photocatalyst and a binder, it is preferable that the binder used has a high binding energy in which the main skeleton is not decomposed by photoexcitation of the photocatalyst. As such a binder, the organopolysiloxane mentioned above is mentioned, for example.

In addition, an amorphous silica precursor can be used as the binder. As the amorphous silica precursor, a silicon compound represented by the chemical formula SiX4 and X is halogen, methoxy group, ethoxy group or acetyl group, silanol which is a hydrolyzate thereof, or polysiloxane having an average molecular weight of 3000 or less is preferable. Specifically, tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetrabutoxysilane, tetramethoxysilane, etc. are mentioned. These can be used individually or in mixture of 2 or more types.

When the photocatalyst treatment layer contains a photocatalyst and a binder, the content of the photocatalyst in the photocatalyst treatment layer can be set within the range of 5% by mass to 60% by mass, preferably in the range of 20% by mass to 50% by mass. Mine

In addition, the photocatalyst treatment layer may contain, in addition to the photocatalyst and the binder described above, for example, the same surfactants and additives as those described in JP-A-2000-249821.

It is preferable that the thickness of a photocatalyst treatment layer exists in the range of 0.01 micrometer-10 micrometers.

In addition, the wettability of the surface of the photocatalyst treatment layer may be lyophilic or liquid repellent.

As a formation method of the photocatalyst treatment layer containing only a photocatalyst, the vacuum film-forming methods, such as a CVD method, a sputtering method, and a vacuum vapor deposition method, are mentioned, for example. By using the vacuum film forming method, it is possible to form a photocatalyst treatment layer which is a uniform film and contains only a photocatalyst. Thereby, it becomes possible to change the wettability of the surface of a wettability change layer uniformly. In addition, since the photocatalyst treatment layer contains only the photocatalyst, the wettability on the surface of the wettability changing layer can be changed more efficiently than in the case of using a binder.

As a method of forming a photocatalyst treatment layer containing only a photocatalyst, for example, when the photocatalyst is titanium dioxide, amorphous titania is formed on a substrate, and then the amorphous titania is converted into crystalline titania by firing. Etc. can be mentioned.

The amorphous titania is, for example, hydrolyzed and dehydrated condensed inorganic salts of titanium such as titanium tetrachloride and titanium sulfate, or tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-propoxycitane, tetrabutoxy Organic titanium compounds, such as titanium and tetramethoxy titanium, can be obtained by hydrolysis and dehydration condensation in the presence of an acid. Subsequently, the amorphous titania can be modified to anatase-type titania by firing at 400 ° C to 500 ° C, and to rutile titania by firing at 600 ° C to 700 ° C.

As a method for forming a photocatalyst treatment layer containing a photocatalyst and a binder, when organopolysiloxane is used as a binder, the photocatalyst layer is dispersed by dispersing the photocatalyst and the organopolysiloxane, which is a binder, with other additives as necessary. Forming coating liquid can be manufactured and the method of apply | coating this coating liquid for photocatalyst treatment layer formation on a base | substrate can be used. Moreover, when the ultraviolet curable component is contained as a binder, it can also harden | cure by irradiating an ultraviolet-ray after application | coating.

As a solvent used at this time, the organic solvent of alcohol type, such as ethanol and isopropanol, is preferable. As a coating method, general methods, such as spin coating, spray coating, dip coating, roll coating, bead coating, can be used.

As a method of forming a photocatalyst treatment layer containing a photocatalyst and a binder, when an amorphous silica precursor is used as a binder, the photocatalyst treatment layer is formed by uniformly dispersing the particles of the photocatalyst and the amorphous silica precursor in a non-aqueous solvent. A coating solution for preparing a photocatalyst, a coating solution for forming a photocatalyst treatment layer on a substrate, hydrolyzing an amorphous silica precursor with moisture in the air to form silanol, and dehydrating polycondensation at room temperature. have. When dehydration polycondensation of silanol is performed at 100 degreeC or more, the polymerization degree of silanol increases and the intensity | strength of a membrane surface can be improved.

As a formation position of a photocatalyst treatment layer, the photocatalyst treatment layer 34 may be formed in the whole surface on the base 32, for example as shown in FIG. 6 (a), For example, FIG. 6 (b) ), The photocatalyst treatment layer 34 may be formed on the substrate 32 in a pattern.

When the photocatalyst treatment layer is formed in a pattern form, the photocatalyst treatment layer is arranged with a predetermined gap with respect to the wettability changing layer, and there is no need for pattern irradiation using a photomask or the like when irradiating energy, Irradiation to the entire surface can change the wettability of the wettability changing layer surface. In addition, since the wettability changes only on the surface of the wettability changing layer facing the photocatalytic treatment layer, as the direction of energy irradiation, any direction may be used if energy is irradiated to the part where the photocatalyst treatment layer and the wettability changing layer face. Furthermore, the irradiated energy is also not limited to being parallel such as parallel light.

It does not specifically limit as the patterning method of this photocatalyst treatment layer, For example, the photolithographic method etc. are mentioned.

(ii) gas

The gas used for a photocatalyst process layer board | substrate selects transparency suitably according to the irradiation direction of the energy mentioned later or the light extraction direction of the EL element obtained.

For example, when the EL element shown in Fig. 5E is a top emission type and the substrate or the first electrode layer in the EL element is opaque, the direction of energy irradiation is necessarily from the photocatalytic treatment layer substrate side. . For example, as shown in FIG.5 (b), the light shielding part 33 is formed in pattern shape in the photocatalyst process layer board | substrate 31, and is patterned using this light shielding part 33. FIG. Even in the case of energy irradiation, it is necessary to irradiate energy from the photocatalyst treatment layer substrate side. Therefore, in these cases, the gas needs to have transparency.

On the other hand, for example, when the EL element shown in Fig. 5E is a bottom emission type, energy can be irradiated from the substrate side in the EL element. Therefore, in this case, transparency is not required for the substrate.

In addition, a base may be flexible, for example, a resin film, etc., and may be a non-flexible, for example, glass substrate.

Although it does not specifically limit as a base | substrate, Since a photocatalyst process layer board | substrate is used repeatedly, it has a predetermined intensity | strength, and the thing whose surface is good adhesiveness with a photocatalyst process layer is used preferably. Specifically, glass, ceramics, metals, plastics, etc. are mentioned as a material which comprises a base body.

In addition, in order to improve the adhesion between the surface of the substrate and the photocatalyst treatment layer, an anchor layer may be formed on the substrate. As a formation material of an anchor layer, a silane type, a titanium coupling agent, etc. are mentioned, for example.

(iii) shading

The light shielding portion may be formed in a pattern on the photocatalyst treatment layer substrate used in the present embodiment. When the photocatalyst treatment layer substrate which has a pattern light shielding part is used, it is not necessary to use a photomask at the time of energy irradiation, or to perform drawing irradiation by a laser beam. Therefore, in this case, since the alignment of the photocatalyst treatment layer substrate and the photomask is unnecessary, it is possible to make a simple process, and the expensive apparatus required for drawing irradiation is also unnecessary, which is advantageous in terms of cost.

As a formation position of a light shielding part, the light shielding part 33 is formed in pattern form on the base | substrate 32, for example as shown to FIG. 5 (b), and the photocatalyst process layer 34 on this light shielding part 33 is carried out. ) May be formed. For example, as shown in FIG. 7, the photocatalyst treatment layer 34 may be formed on the base 32, and the light shielding part 33 may be formed in a pattern form on the photocatalyst treatment layer 34. FIG. have. In addition, although not shown, the light shielding portion may be formed in a pattern on the surface of the side on which the gas photocatalyst treatment layer is not formed.

When the light shielding portion is formed on the substrate and the light shielding portion is formed on the photocatalyst treatment layer, the photocatalyst treatment layer and the wettability changing layer have a gap between the photocatalyst treatment layer and the wettability changing layer. Since the light shielding portion is disposed in the vicinity, the influence of energy scattering in the gas or the like can be reduced. Therefore, the pattern irradiation of energy can be performed very accurately.

In the case where the light shielding portion is formed on the photocatalyst treatment layer, when the photocatalyst treatment layer and the wettability varying layer are arranged with a predetermined gap, the gap is formed by matching the film thickness of the light shielding portion with the distance of the gap. A light shielding part can be used as a spacer for making it constant. That is, when arranging the photocatalyst treatment layer and the wettability varying layer at a predetermined gap, the predetermined gap can be maintained by arranging the light shielding portion and the wettability varying layer in close contact. Further, by irradiating energy from the photocatalytic treatment layer substrate in this state, the wettability change pattern can be formed on the wettability change layer surface with high accuracy.

In the case where the light shielding portion is formed on the surface of the side where the gas photocatalyst treatment layer is not formed, the photomask can be adhered to the surface of the light shielding portion to such an extent that the light mask can be detachably attached. It is preferable to change to a small.

It does not specifically limit as a formation method of a light shielding part, It selects suitably according to the characteristic of the formation surface of a light shielding part, shielding against energy required, etc.

For example, a light shielding portion can be formed by forming a metal thin film such as chromium having a thickness of about 1000 Pa to 2000 Pa by a sputtering method, a vacuum deposition method, or the like, and patterning the thin film. As this patterning method, a general patterning method can be used.

For example, a light shielding part can also be formed by patterning the layer which contained light-shielding particle | grains, such as carbon microparticles, a metal oxide, an inorganic pigment, and an organic pigment, in a resin binder. Examples of the resin binder include polyimide resins, acrylic resins, epoxy resins, polyacrylamides, polyvinyl alcohols, gelatin, casein, cellulose and the like. These resin can be used individually by 1 type or in mixture of 2 or more types. Moreover, as a resin binder, photosensitive resin or O / W emulsion type resin composition, for example, the thing which emulsified reactive silicone, etc. can be used. As a patterning method, general patterning methods, such as a photolithography method and a printing method, can be used.

The thickness of the light shielding part using a resin binder can be set within the range of 0.5 micrometer-10 micrometers.

(iv) primer layer

In the present embodiment, when the light shielding portion is formed in a pattern shape on the substrate as described above, and the photocatalyst treatment layer is formed on the light shielding portion, for example, as shown in FIG. 8, the light shielding portion 33 is shown. It is preferable that the primer layer 35 is formed between and the photocatalyst treatment layer 34.

Although the function and function of this primer layer are not clear, the primer layer patterns impurities, especially the light shielding part, from the light-shielding part and the opening part which exist between the light-shielding parts which become a factor which inhibits the change of the wettability of the wettability-changing layer by the action of a photocatalyst. It is considered to have a function of preventing the diffusion of residues and impurities such as metals and metal ions generated in the process. Therefore, by forming a primer layer between the light shielding portion and the photocatalyst treatment layer, the treatment of wettability change proceeds with high sensitivity, and as a result, a wettability change pattern with high resolution can be obtained.

Since it is thought that the impurity which exists not only in a light shielding part but an opening part between light shielding parts affects the action of a photocatalyst, the primer layer is formed in the whole surface so that the opening of a patterned light shielding part and a light shielding part may be covered. desirable. In addition, the primer layer may be disposed so that the photocatalyst treatment layer and the light shielding portion do not physically contact each other.

Although it does not specifically limit as a material which comprises this primer layer, The inorganic material which is hard to decompose by the action of a photocatalyst is preferable. As an inorganic material, amorphous silica is mentioned, for example. As a precursor of this amorphous silica, a silicon compound represented by the formula SiX4, X is halogen, methoxy group, ethoxy group or acetyl group, silanol which is a hydrolyzate thereof, or polysiloxane having an average molecular weight of 3000 or less is preferably used.

The film thickness of the primer layer is preferably in the range of 0.001 µm to 1 µm, and particularly preferably in the range of 0.001 µm to 0.5 µm.

(2) Arrangement of the photocatalytic treatment layer substrate and the wettability changing layer

In the present embodiment, the photocatalyst treatment layer substrate is disposed with respect to the wettability varying layer with a gap between the action of the photocatalyst due to energy irradiation. Typically, the photocatalytic treatment layer and the wettability varying layer of the photocatalytic treatment layer substrate are arranged in the wettability varying layer with a gap in which the action of the photocatalyst due to energy irradiation can occur.

The gap also includes a state in which the photocatalyst treatment layer and the wettability varying layer are in contact with each other.

It is preferable that the space | interval of a photocatalyst treatment layer and a wettability change layer is 200 micrometers or less specifically ,. By arranging the photocatalyst treatment layer and the wettability changing layer at predetermined intervals, active oxygen species generated by oxygen, water, and photocatalysis are easily desorbed. When the space | interval of a photocatalyst treatment layer and a wettability change layer is wider than the said range, the active oxygen species generate | occur | produced by the photocatalysis becomes difficult to contact a wettability change layer, and there exists a possibility of slowing the change rate of wettability. On the contrary, when the space | interval of a photocatalyst treatment layer and a wettability change layer is too narrow, active oxygen species generate | occur | produced by oxygen, water, and photocatalysis will become difficult to desorb, and as a result, the change rate of wettability may be slowed down.

The interval is more preferably within the range of 0.2 μm to 20 μm, more preferably 1 μm to 10 μm, considering that the pattern accuracy is very good, the sensitivity of the photocatalyst is high, and the efficiency of the change in wettability is good. In range

On the other hand, in the case of manufacturing a large area EL element of 300 mm x 300 mm, for example, it is very difficult to provide such a fine gap between the photocatalytic treatment layer substrate and the wettability changing layer. Therefore, when manufacturing a relatively large area EL element, it is preferable that the said clearance exists in the range of 5 micrometers-100 micrometers, More preferably, it exists in the range of 10 micrometers-75 micrometers. It is because deterioration of pattern precision, such as a pattern being blurred, can be suppressed by making the said gap into the said range, and it can suppress that the sensitivity of a photocatalyst deteriorates and the efficiency of wettability change deteriorates.

When energy is irradiated with respect to the relatively large area as described above, the setting of the gap in the positioning device of the photocatalytic treatment layer substrate and the wettability varying layer in the energy irradiation apparatus is within the range of 10 µm to 200 µm, in particular. It is preferable to set in the range of 25 micrometers-75 micrometers. This is because the setting value of the gap in the above range can be arranged without causing the photocatalyst treatment layer substrate and the wettability changing layer to come into contact with each other without causing a significant reduction in pattern accuracy or a significant deterioration in the sensitivity of the photocatalyst. .

In the present embodiment, such a spaced arrangement may be maintained only at least during energy irradiation.

As a method of arrange | positioning such a very narrow gap uniformly and arrange | positioning a photocatalyst treatment layer and a wettability change layer, the method of using a spacer is mentioned, for example. As a method of using a spacer, a uniform gap can be formed, and at the same time, the portion in contact with the spacer has the same pattern as the wettability change pattern described above because the action of the photocatalyst does not reach the surface of the wettability change layer. By having it, it becomes possible to form a predetermined wettability change pattern on the surface of a wettability change layer.

In the present embodiment, the spacer may be formed as one member, but the spacer is preferably formed on the photocatalytic treatment layer of the photocatalytic treatment layer substrate for the purpose of simplifying the process. In this case, it has an advantage as described in the above-mentioned light shielding section.

The spacer may have a function of protecting the wettability changing layer surface such that the action of the photocatalyst does not reach the wettability changing layer surface. Therefore, the spacer may not have shielding against the energy to be irradiated.

(3) energy survey

In this embodiment, after arrange | positioning a photocatalyst treatment layer and a wettability change layer with a predetermined gap, pattern wettability change pattern is formed in the surface of a wettability change layer by pattern irradiation of energy from a predetermined direction.

In addition, since the wavelength and the light source of light used for energy irradiation are the same as that of the said 1st Embodiment, description here is abbreviate | omitted.

The irradiation amount of energy at the time of energy irradiation is made into the irradiation amount required for the wettability of the surface of a wettability change layer to change by the action of the photocatalyst in a photocatalyst treatment layer.

At this time, it is preferable to perform energy irradiation while heating the photocatalyst treatment layer. It is because a sensitivity can be raised and a wettability can be changed efficiently. Specifically, heating in the range of 30 ° C to 80 ° C is preferable.

The direction of energy irradiation is determined depending on whether or not a light shielding portion is formed on the photocatalyst treatment layer substrate, the light extraction direction of the EL element, or the like.

For example, when the light shielding part is formed in the photocatalyst treatment layer substrate, and the gas of the photocatalyst treatment layer substrate is transparent, energy irradiation is performed from the photocatalyst treatment layer substrate side. In this case, when the light shielding portion is formed on the photocatalyst treatment layer, and the light shielding portion functions as a spacer, the energy irradiation direction may be from the photocatalyst treatment layer substrate side or may be from the substrate side.

For example, when the photocatalyst treatment layer is formed in a pattern, the direction of energy irradiation may be any direction as long as energy is irradiated to the portion where the photocatalyst treatment layer and the wettability changing layer face each other as described above.

Similarly, even when the above-mentioned spacer is used, if energy is irradiated to the part where the photocatalyst treatment layer and the wettability change layer face each other, the direction of energy irradiation may be any direction.

For example, when using a photomask, energy is irradiated from the side in which the photomask is arrange | positioned. In this case, the side on which the photomask is disposed needs to be transparent.

After energy irradiation, the photocatalyst treated layer substrate is removed from the wettability changing layer.

(4) wettability change pattern

The wettability change pattern in this embodiment is formed in the wettability change layer surface, and contains a lyophilic region and a liquid repellent region.

In addition, since it is the same as that of what was described in the said 1st Embodiment about the contact angle with the liquid in a lyophilic region and a liquid repellent region, description here is abbreviate | omitted.

3. Other Process

Also in this embodiment, like a said 1st Embodiment, a hole injection transport layer formation process, an electron injection transport layer formation process, an insulation layer formation process, etc. can be performed.

In addition, similarly to the first embodiment, the second electrode layer forming step is usually performed.

B. EL device

The EL element of the present invention is formed on a substrate, a first electrode layer formed in a pattern shape on the substrate, and on the first electrode layer, and the wettability is changed by the action of a photocatalyst due to energy irradiation, and the first surface is formed on the surface. Wettability change with a wettability change pattern disposed over the pattern of the electrode layer, the lyophilic region containing polysiloxane and the liquid repellency region disposed over the opening of the pattern of the first electrode layer and containing the organopolysiloxane containing fluorine; The quantum dot which has a layer, the light emitting layer formed on the lyophilic region of the said wettability change layer, and the 2nd electrode layer formed on the said light emitting layer, and arrange | positioned the silane coupling agent around the said light emitting layer is used, It is characterized by the above-mentioned.

In the EL element illustrated in FIG. 1E, the first electrode layer 2 is formed in a pattern on the substrate 1, and the insulating layer 3 is formed in the opening of the pattern of the first electrode layer 2. The wettability changing layer 4 is formed on the first electrode layer 2 and the insulating layer 3, and includes a lyophilic region 5 and a liquid-repellent region 6 on the surface of the wettability changing layer 4. The wettability change pattern is formed, the light emitting layer 7 is formed on the lyophilic region 5, and the second electrode layer 8 is formed on the light emitting layer 7. The lyophilic region 5 on the surface of the wettability changing layer 4 contains polysiloxane and is disposed on the pattern of the first electrode layer 2. Further, the liquid-repellent region 6 on the surface of the wettability changing layer 4 contains an organopolysiloxane containing fluorine, and is disposed on the opening of the pattern of the first electrode layer 2, that is, on the insulating layer 3 have.

Here, fluorine has very low surface energy. Therefore, the surface of the substance containing much fluorine becomes smaller in critical surface tension. That is, compared with the critical surface tension of the surface of the part with high fluorine content, the critical surface tension of the part with little fluorine content becomes large.

In the present invention, since the lyophilic region on the surface of the wettability changing layer contains polysiloxane, and the liquid repellency region on the surface of the wettability changing layer contains organopolysiloxane including fluorine, the fluorine content of the liquid repellency region is lyophilic. It can be said that it is large compared with fluorine content of a region. Therefore, it can be said that the critical surface tension of the lyophilic region is larger than the critical surface tension of the liquid repellent region.

As described above, since the liquid repellent region and the lyophilic region have different critical surface tensions, that is, wettability, the light emitting layer can be formed only on the lyophilic region using the difference in the wettability between the liquid repellent region and the lyophilic region. Therefore, it can be set as an EL element which can easily pattern a light emitting layer, without requiring a complicated patterning process and expensive vacuum equipment.

In addition, in the invention, since the quantum dots in which the silane coupling agent is disposed around the light emitting layer are used, the light emitting layer can be cured, and the stability of the quantum dots in the light emitting layer can be improved, and the life characteristics are improved. It is possible to improve. Furthermore, the thermal stability (Tg: glass transition temperature) of a light emitting layer can also be improved. In addition, since the silane coupling agent is relatively easy in molecular design, it is possible to improve the life characteristics by using a silane coupling agent having a functional group exhibiting various functionalities.

Also, a quantum dot in which the lyophilic region on the surface of the wettability-changing layer contains polysiloxane, the liquid-repellent region on the surface of the wettability-changing layer contains organopolysiloxane containing fluorine, and the luminescent layer has a silane coupling agent disposed around the light-emitting layer Since it is used, the organopolysiloxane in a wettability change layer couple | bonds with a 1st electrode layer, and the silane coupling agent in a light emitting layer couple | bonds with a wettability change layer, and the adhesiveness of a 1st electrode layer, a wettability change layer, and a light emitting layer can be improved. Thereby, it is possible to prevent the fall of the life characteristic by the interlayer peeling etc. at the time of EL element drive etc.

In addition, "using a quantum dot in which a silane coupling agent is arrange | positioned around a light emitting layer" means that when the silane coupling agent arrange | positioned around a quantum dot is a silane coupling agent itself in a light emitting layer, It includes both the case of the hydrolyzate and the case of the hydrolysis condensate of the silane coupling agent. That is, in the light emitting layer, a silane coupling agent itself may be disposed around the quantum dot, a hydrolyzate of the silane coupling agent may be disposed, or a hydrolysis condensate of the silane coupling agent may be disposed. Moreover, the silane coupling agent itself, the hydrolyzate of a silane coupling agent, and the hydrolysis-condensation product of a silane coupling agent may be mixed.

When the light emitting layer contains a hydrolysis condensate of a silane coupling agent, the light emitting layer can be made cured. Accordingly, when forming the hole injection transport layer, the electron injection transport layer, or the like using the coating solution on the light emitting layer, the light emitting layer is not dissolved in the solvent in the coating solution for forming the hole injection transport layer, the electron injection transport layer, or the like, and stably rests on the light emitting layer. A hole injection transport layer or an electron injection transport layer can be laminated.

In addition, since the board | substrate, the 1st electrode layer, the light emitting layer, and the 2nd electrode layer were described in detail in the said "A. EL element manufacturing method", the description here is abbreviate | omitted. Hereinafter, the other structure of the EL element of this invention is demonstrated.

1. Wetability changing layer

The wettability changing layer in the present invention is formed on the first electrode layer, and the wettability is changed by the action of the photocatalyst due to energy irradiation. Further, the wettability varying layer is disposed on the surface of the pattern of the first electrode layer and is disposed on the lipophilic region containing polysiloxane and the opening of the pattern of the first electrode layer, and the liquid repellency containing organopolysiloxane containing fluorine is included. It has a wettability change pattern that includes a region.

The lyophilic region and the liquid repellent region are described in the section of the wettability change pattern forming step of the first embodiment of the "A. EL device manufacturing method", and therefore the description thereof is omitted.

The liquid repellent region contains organopolysiloxane containing fluorine, and the lyophilic region contains polysiloxane. As described above, since fluorine has a very low surface energy, the surface of the fluorine-containing material has a smaller critical surface tension. Therefore, it can be said that the fluorine content of the liquid repellent region is higher than the fluorine content of the lyophilic region, and the critical surface tension of the lyophilic region is larger than the critical surface tension of the liquid repellent region. Since the wettability-changing layer has a wettability change pattern including such a liquid-repellent region and a lyophilic region on its surface, when the light emitting layer is formed on the wettability-changing layer, the wettability-changing layer is formed by using the wettability difference between the liquid-repellent region and the lyophilic region. The light emitting layer can be formed only on the liquid region.

The fluorine content in the lyophilic region and the liquid-repellent region is described in the section of the wettability change pattern forming step of the first embodiment of the "A. EL device manufacturing method", and therefore the description thereof is omitted.

Examples of organopolysiloxanes containing fluorine constituting the liquid repellent region include (1) organopolysiloxanes which exhibit great strength by hydrolyzing and polycondensing chloro or alkoxysilanes by sol-gel reaction and the like, and (2) water repellency and The organopolysiloxane which bridge | crosslinked the reactive silicone excellent in oil repellency is mentioned. Such fluorine-containing organopolysiloxane is a material whose wettability is changed by the action of a photocatalyst due to energy irradiation, and has a main chain that is hardly deteriorated and decomposed by the action of the photocatalyst, and thus is preferably used in a liquid repellent region. It can be.

In the case of (1), as organopolysiloxane containing fluorine, the following general formula

YnSiX (4-n)

(Wherein Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, and when Y is a fluoroalkyl group, X represents an alkoxyl group, an acetyl group or a halogen, and Y represents an alkyl group, a vinyl group, an amino group) , In the case of a phenyl group or an epoxy group, X represents fluorine and n is an integer of 0 to 3).

It is preferable that it is 1 type, or 2 or more types of hydrolysis condensate or cohydrolysis condensate among the silicon compounds represented by these. It is preferable that carbon number of group represented by Y exists in the range of 1-20. Moreover, it is preferable that the alkoxyl group represented by X is a methoxy group, an ethoxy group, a propoxy group, butoxy group. As a silicon compound represented by the said chemical formula, the thing specifically described in Unexamined-Japanese-Patent No. 2000-249821 can be used.

In particular, the organopolysiloxane containing fluorine is preferably a polysiloxane containing a fluoroalkyl group. Examples of the polysiloxane containing a fluoroalkyl group include one or two or more hydrolysis condensates or cohydrolysis condensates of the fluoroalkylsilanes described in JP-A-2000-249821. Generally what is known as a fluorine-type silane coupling agent can be used.

When the polysiloxane containing a fluoroalkyl group is used, since the liquid repellency of the liquid repellent region is greatly improved, film formation of the light emitting layer to the liquid repellent region can be prevented, and the light emitting layer can be formed only in the lyophilic region.

The polysiloxane containing a fluoroalkyl group in the liquid-repellent region can be confirmed using X-ray photoelectron spectroscopy, Rutherford backscattering spectroscopy, nuclear magnetic resonance spectroscopy or mass spectrometry.

In addition, in the case of said (2), as reactive silicone used for the organopolysiloxane containing fluorine, the compound which has frame | skeleton represented by a following formula is mentioned.

Here, n is an integer of 2 or more, R <^1> , R <^2> is a C1-C10 substituted or unsubstituted alkyl group, alkenyl group, an aryl group, or a cyanoalkyl group, and 40% or less of the whole is molar ratio phenyl fluoride. In addition, it is preferable that R ¹ and R ² be a methyl group because the surface energy is the smallest, and it is more preferable that the methyl group is 60% or more in molar ratio. The chain terminal or side chain has a reactive group such as at least one or more hydroxyl groups in the molecular chain.

The liquid repellent region may also contain a stable organosilicon compound that does not undergo crosslinking reaction such as dimethylpolysiloxane together with the organopolysiloxane containing fluorine described above.

The lyophilic region is a region with less fluorine content than the liquid repellent region. For example, as shown in Figs. 1B, 5C, 5B, and 5C, fluorine is used in the irradiated portion of the wettability change layer 4 due to the action of a photocatalyst according to energy irradiation. Wetting property changes so that the side chain containing the fluorine of the organopolysiloxane containing may decompose | disassemble, and fluorine content will fall and a contact angle with a liquid may fall. Thus, as polysiloxane which comprises a lyophilic region, the side chain containing the fluorine of the organopolysiloxane containing said fluorine was decomposed by the action of the photocatalyst by energy irradiation.

In addition, the lyophilic region may contain a stable organosilicon compound that does not undergo a crosslinking reaction such as dimethylpolysiloxane together with the polysiloxane, similarly to the liquid repellent region.

In addition, the liquid-repellent region and the lyophilic region may contain, in addition to the organopolysiloxane and polysiloxane containing fluorine described above, for example, the same surfactants and additives as those described in JP-A-2000-249821. It may be.

The position where the liquid repellent region and the lyophilic region are formed may be such that the liquid repellent region is disposed over the opening of the pattern of the first electrode layer, and the lyophilic region may be disposed over the pattern of the first electrode layer.

In addition, as a pattern shape of a liquid repellent region and a lyophilic region, it is suitably selected according to the pattern shape of a 1st electrode layer. For example, when the first electrode layer is formed in a stripe shape, the lyophilic region is also formed in a stripe shape corresponding to the stripe pattern of the first electrode layer. In addition, for example, when the first electrode layer is formed in a mosaic shape corresponding to the pixel, the lyophilic region may be formed in a stripe shape or may be formed in a mosaic shape. In any case, regions other than the lyophilic region on the surface of the wettability changing layer become liquid repellent regions.

The wettability changing layer may have a wettability change pattern including the liquid-repellent region and the lyophilic region described above on its surface. Usually, in the wettability changing layer, portions other than the lyophilic region of the surface have the same structure as the liquid-repellent region of the surface. That is, in the wettability changing layer, portions other than the hydrophilic region on the surface contain organopolysiloxane containing fluorine.

In addition, the wettability changing layer may or may not contain a photocatalyst. The wettability changing layer containing a photocatalyst is the same as the wettability changing layer in 1st Embodiment of "A. EL element manufacturing method." In addition, the wettability change layer which does not contain a photocatalyst is the same as the wettability change layer in 2nd Embodiment of "A. EL element manufacturing method."

In addition, when the wettability change layer contains a photocatalyst, the formation method of the wettability change layer and the like are described in detail in the first embodiment of "A. EL device manufacturing method", and the wettability change layer does not contain the photocatalyst. In this case, the method of forming the wettability changing layer and the like are described in detail in the second embodiment of "A. EL device manufacturing method", and thus the description thereof is omitted.

In addition, since the film thickness of a wettability change layer etc. were described in detail in the said "A. manufacturing method of an EL element", the description here is abbreviate | omitted.

2. Other layers

In the present invention, a hole injection transport layer may be formed between the first electrode layer and the light emitting layer.

In addition, when the hole injection transport layer is a hole transport layer, the hole transport layer and the light emitting layer may be phase separated. This is because the luminous efficiency and lifespan characteristics are further improved.

In addition, since the hole injection transport layer, the hole transport layer, and the light emitting layer are phase-separated, they are described in detail in "A. EL element manufacturing method", and thus the description thereof is omitted.

Further, in the present invention, an electron injection transport layer may be formed between the light emitting layer and the second electrode layer. In addition, since the electron injection transport layer was described in "A. EL element manufacturing method", the description here is omitted.

In addition, an insulating layer may be formed in the opening of the pattern of the first electrode layer on the substrate. In addition, about the insulating layer, since it described in the "A. EL element manufacturing method", the description here is abbreviate | omitted.

In addition, this invention is not limited to the said embodiment. The said embodiment is an illustration, Any thing which has a structure substantially the same as the technical idea described in the claim of this invention, and exhibits the same effect is included in the technical scope of this invention.

<Example>

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely using an Example.

Example 1

(Formation of the transparent electrode)

The ITO film | membrane was formed into a film thickness of 1500 kPa by the sputtering method on the cleaned glass substrate as a transparent electrode. Thereafter, the ITO film was patterned by the photolithography method so as to have a line width of 300 m and a pitch of 100 m.

(Formation of insulating layer)

A negative resist (V259PA manufactured by Shinnitetsu Chemical Co., Ltd., V259PA) was applied to the substrate on which the ITO film was formed in a pattern shape by spin coating so as to have a dry film thickness of 1 μm, and then fired at 120 ° C. for 1 hour. Thereafter, 365 nm UV light was exposed at an exposure dose of 500 mJ through a photomask with a width of 100 μm around the pitch portion without the ITO film. At this time, the photomask and the substrate were exposed with a gap of 1 mm. This was developed for 40 seconds with an organic alkali developer (V259OD manufactured by Shinnitetsu Chemical Co., Ltd.), and then fired at 160 ° C. for 1 hour to form an insulating layer.

(Formation of the wettability changing layer)

The coating liquid for wettability changing layer formation was manufactured by mixing the following components.

<Composition of Coating Liquid for Forming Wetting Change Layer>

ㆍ 3 parts by weight of titanium dioxide sol liquid (STS-01 manufactured by Ishihara Sangyo Co., Ltd.)

ㆍ 1 part by weight of tetraethoxysilane

ㆍ 40 parts by weight of hydrochloric acid according to 2 regulations

ㆍ 75 parts by weight of isopropyl alcohol

7.5 parts by weight of fluoroalkoxysilane (MF-160E manufactured by Tochem Products Co., Ltd.)

The coating liquid for wettability changing layer formation was apply | coated on the said board | substrate with a spin coater, and the drying process was performed at 150 degreeC for 10 minutes, and the transparent wettability changing layer with a film thickness of 60 nm was formed. The wetness change layer was irradiated with a high pressure mercury lamp (254 nm, 365 nm) for 50 seconds using a high pressure mercury lamp (254 nm, 365 nm) to form a wettability change pattern including a lyophilic region and a liquid-repellent region.

(Formation of light emitting layer)

A dispersion of red luminescent quantum dots (Maple-Red Orange, manufactured by Evidence Technology), and a dispersion of green luminescent quantum dots (Adirondack Green, manufactured by Evidence Technology, Inc.) on the lyophilic region. ) And a dispersion of blue colored quantum dots (Lake Placid Blue manufactured by Avid Technologies) were applied by inkjet method, and dried at 80 ° C. for 30 minutes to form three color light emitting layers in a pattern form. .

(Formation of the electron transport layer)

20 nm of TAZ was formed by the vacuum evaporation method on the said light emitting layer, and 20 nm of Alq3 were formed subsequently.

(Formation of metal electrodes)

Thereafter, a LiF film (film thickness of 5 nm) and an Al film (film thickness of 1000 kPa) were formed by a vacuum deposition method by a mask vapor deposition method. At this time, a LiF film and an Al film were formed in a pattern so as to be orthogonal to the pattern of the ITO film. The EL element was manufactured by the above.

(evaluation)

The ITO electrode and the Al electrode were provided with terminals, and they were connected to the voltage source. When a voltage exceeding 5 V was applied, light emission with a peak at 620 nm in the red light emitting layer, 520 nm in the green light emitting layer, and 490 nm in the blue light emitting layer was obtained. This showed the same light emission as the photoluminescence spectrum of CdSe / ZnS quantum dots of each color protected by TOPO. In addition, in the obtained EL element, good stability, efficiency, and brightness were obtained, and good patterning titration was confirmed.

Example 2

In Example 1, an EL device was manufactured in the same manner as in Example 1 except that the light emitting layer was formed as follows.

(Formation of light emitting layer)

1. Preparation of Coating Solution for Forming Red Light Emitting Layer

A silane coupling agent was added to the dispersion of red luminescent quantum dots (Maple-Red Orange manufactured by Avid Technologies, Inc.), and the ligand was substituted.

Specifically, first, 5 g of tetramethoxysilane (LS-540, manufactured by Shin-Etsu Chemical Co., Ltd.), 1 g of phenyltrimethoxysilane (LS-2750, manufactured by Shin-Etsu Chemical Co., Ltd.), and 0.01 N 2 g of HCl was stirred at room temperature for 12 hours to obtain a copolymer compound (silane coupling agent). Toluene was added to this copolymerization compound, and it stirred and dissolved, and obtained the 10 weight% toluene solution of the silane coupling agent.

Subsequently, 2 g of a 10 wt% toluene solution of the silane coupling agent was added dropwise at room temperature (26 ° C) while stirring 1 g of the dispersion solution of the quantum dots under argon gas atmosphere. After stirring this reaction liquid for 12 hours, it changed from argon gas atmosphere to atmospheric atmosphere, adds the amount of toluene evaporated and scattered, and 8g of ethanol was dripped. Subsequently, the precipitate was separated from the reaction solution by centrifugation, and then purified by reprecipitation by the procedure shown below.

That is, the precipitate was mixed with 4 g of toluene to obtain a dispersion, and purified precipitate was obtained by dropwise adding 10 g of ethanol to the dispersion.

The purified product of the quantum dots protected by the silane coupling agent was obtained by centrifuging the reprecipitation liquid obtained in this way.

Next, the coating liquid for red luminescent layer formation which disperse | distributed the quantum dot protected by the said silane coupling agent in toluene was prepared.

2. Preparation of Coating Solution for Forming Green Emitting Layer

The coating liquid for green light emitting layer formation was produced like manufacture of the above-mentioned red light emitting layer formation coating liquid using the dispersion liquid of green luminescence quantum dot (adirondack green by Aviation Technology).

3. Preparation of Coating Solution for Forming Blue Emitting Layer

The coating liquid for blue light emitting layer formation was produced like manufacture of the above-mentioned coating liquid for red light emitting layer formation using the dispersion liquid of blue luminescence quantum dot (Lave Placid Blue by Aviation Technology).

4. Formation of light emitting layer

The above-mentioned coating solution for forming a red light-emitting layer, coating solution for forming a green light-emitting layer, and coating solution for forming a blue light-emitting layer were applied by an inkjet method, dried at 100 ° C. for 30 minutes, and cured to form three light-emitting layers in a pattern form. .

(evaluation)

The ITO electrode and the Al electrode were provided with terminals, and they were connected to the voltage source. When a voltage exceeding 4 V was applied, light emission with a peak at 620 nm in the red light emitting layer, 520 nm in the green light emitting layer, and 490 nm in the blue light emitting layer was obtained. This showed the same light emission as the photoluminescence spectrum of CdSe / ZnS quantum dots of each color protected by TOPO. In addition, in the obtained EL element, good stability, efficiency, and brightness were obtained, and good patterning titration was confirmed.

Example 3

(Formation of insulating layer)

First, a substrate on which a ITO film was patterned on a glass substrate with a line width of 80 μm, a space width of 20 μm, and a pitch of 100 μm was prepared.

Subsequently, a positive photosensitive material (OFPR-800, manufactured by TOKYO Corporation) was applied to the entire surface of the substrate by a spin coating method so as to have a film thickness of 1.5 mu m to form an insulating film. Subsequently, exposure is performed using a photomask designed so that the opening of the light shielding portion is a rectangle having a width of 70 μm and a width of 70 μm in accordance with the pattern of the ITO film, followed by development with an alkaline developer (NMD-3, manufactured by Toh-Oh Ko Corporation). It was. Subsequently, the heat-hardening process for 30 minutes was performed at 250 degreeC, and it was set as the insulating layer.

(Formation of the wettability changing layer)

Next, the coating liquid for wettability changing layer formation of the following composition was manufactured.

<Composition of Coating Liquid for Forming Wetting Change Layer>

ㆍ 0.4 parts by mass of organoalkoxysilane (GE Toshiba Silicone Co., Ltd., TSL8113)

0.3 parts by mass of fluoroalkylsilane (GE Toshiba Silicone Co., Ltd., TSL8233)

ㆍ 480 parts by mass of isopropyl alcohol

This wettability-forming layer-forming coating solution was applied onto the substrate by spin coating, subjected to heating and drying treatment at 150 ° C. for 10 minutes to proceed with hydrolysis and polycondensation reactions, and cured to have a film thickness of 10 nm. A wettability varying layer was formed.

(Production of Photocatalyst Treatment Layer Substrate)

Next, a photomask designed to have a rectangular opening having a width of 85 µm and a width of 85 µm in length was prepared in accordance with the pattern of the ITO film. The coating liquid for photocatalyst treatment layer formation of the following composition is apply | coated on this photomask by a spin coater, it heat-drys for 10 minutes at 150 degreeC, hydrolyzes and polycondensation reaction, it advances and hardens, The catalyst formed a transparent photocatalytic treatment layer with a film thickness of 2000 Pa, which was firmly fixed in the organosiloxane.

<Composition of Coating Liquid for Forming Photocatalyst Treatment Layer>

ㆍ 2 parts by mass of titanium dioxide (manufactured by Ishihara Sangyo Co., Ltd., ST-K01)

ㆍ 0.4 parts by mass of organoalkoxysilane (GE Toshiba Silicone Co., Ltd., TSL8113)

ㆍ Isopropyl Alcohol 3 parts by mass

(Formation of wettability change pattern)

Subsequently, the light source has a high-pressure mercury lamp as a light source, and the photocatalyst layer substrate and the ultraviolet light exposure apparatus having the position adjusting mechanism of the substrate face each other so that the opening of the light shielding portion of the photocatalyst treatment layer substrate and the pattern of the ITO film of the substrate face each other. After adjusting the position of the catalyst treatment layer substrate and the substrate, and adjusting the distance between the photocatalyst treatment layer and the wettability changing layer to be 20 μm, the light exposure amount of 253 nm from the back side of the photocatalyst treatment layer substrate was 200 mJ / It exposed to 2 cm <2>.

The contact angle with the liquid of the exposed part and the unexposed part of a wettability change layer was measured by the contact angle meter (made by Kyowa Chemical Co., Ltd.). It was less than 20 degrees with respect to toluene in an exposed part (liquid lyophilic area | region), and 35 degrees or more with respect to toluene in an unexposed part (liquid-free area).

(Formation of light emitting layer)

The coating solution for forming a blue light emitting layer, the coating solution for forming a green light emitting layer, and the coating solution for forming a red light emitting layer, which were used in Example 2, were applied on the lyophilic region, which is the exposed portion of the wettability-changing layer, by an inkjet method, and at 30 ° C. in air. Drying was performed for three minutes to form three color light emitting layers.

(Formation of the electron transport layer)

20 nm of TAZ was formed by the vacuum evaporation method on the said light emitting layer, and 20 nm of Alq3 were formed subsequently.

(Formation of metal electrodes)

Thereafter, a LiF film (film thickness of 5 nm) and an Al film (film thickness of 1000 kPa) were formed by a vacuum deposition method by a mask vapor deposition method. At this time, a LiF film and an Al film were formed in a pattern so as to be orthogonal to the pattern of the ITO film. The EL element was manufactured by the above.

(evaluation)

The ITO electrode and the Al electrode were provided with terminals, and they were connected to the voltage source. When a voltage exceeding 5 V was applied, light emission with a peak at 620 nm in the red light emitting layer, 520 nm in the green light emitting layer, and 490 nm in the blue light emitting layer was obtained. This showed the same light emission as the photoluminescence spectrum of CdSe / ZnS quantum dots of each color protected by TOPO. In addition, in the obtained EL element, good stability, efficiency, and brightness were obtained, and good patterning titration was confirmed.

Example 4

In Example 3, an EL device was manufactured in the same manner as in Example 3, except that the hole injection layer was formed on the lyophilic region that is the exposed portion of the wettability-changing layer before the light emitting layer was formed.

(Formation of Hole Injection Layer)

Subsequently, an aqueous dispersion of poly (3,4-alkenedioxythiophene) and a salt of polystyrenesulfonic acid (PEDOT / PSS) (Baytron P CH-8000, manufactured by Stalk) is diluted with isopropyl alcohol, A coating liquid for forming a hole injection layer was prepared. The viscosity and surface tension of the coating liquid for hole injection layer formation were measured, and the viscosity was 7 mPa * s and surface tension was 37 dyn / cm. The coating liquid for forming a hole injection layer was applied on the lyophilic region, which is an exposed portion of the wettability changing layer, by an inkjet method so that the film thickness after drying was 80 nm, and dried at 150 ° C. for 10 minutes in air to form a hole injection layer. .

(evaluation)

The ITO electrode and the Al electrode were provided with terminals, and they were connected to the voltage source. When a voltage exceeding 4 V was applied, light emission with a peak at 620 nm in the red light emitting layer, 520 nm in the green light emitting layer, and 490 nm in the blue light emitting layer was obtained. This showed the same light emission as the photoluminescence spectrum of CdSe / ZnS quantum dots of each color protected by TOPO. In addition, in the obtained EL element, good stability, efficiency, and brightness were obtained, and good patterning titration was confirmed.

Example 5

An EL device was fabricated in the same manner as in Example 3 except that the light emitting layer was formed as follows in Example 3, and the electron transporting layer was not formed.

(Formation of light emitting layer)

1. Preparation of Coating Solution for Forming Red Light Emitting Layer

In Example 2, a quantum dot protected with a silane coupling agent manufactured using a dispersion of red luminescent quantum dots (Maple-Red Orange, manufactured by Avid Technologies, Inc.), triazole (electron transport material), and TPD ( A coating solution for forming a red light emitting layer in which a hole transport material) was dispersed in toluene was prepared. At this time, the mixing ratio of each material was 40 mass parts of quantum dots, 30 mass parts of triazoles, and 30 mass parts of TPD which were protected by the silane coupling agent.

2. Preparation of Coating Solution for Forming Green Emitting Layer

In Example 2, a quantum dot protected with a silane coupling agent manufactured using a dispersion of green luminescent quantum dots (Adiron Technology Green, manufactured by Avid Technologies, Inc.) was used, and was the same as the coating liquid for forming a red light-emitting layer. Thus, a coating solution for forming a green light emitting layer was prepared.

3. Preparation of Coating Solution for Forming Blue Emitting Layer

In Example 2, a coating solution for forming a red light-emitting layer was formed by using a quantum dot protected by a silane coupling agent prepared using a dispersion of blue-emitting quantum dots (Lake Placid Blue manufactured by Avid Technology). In the same manner, a coating solution for forming a blue light emitting layer was prepared.

4. Formation of light emitting layer

The above-described coating solution for forming a blue light emitting layer, coating solution for forming a green light emitting layer, and coating solution for forming a red light emitting layer on the lyophilic region, which is an exposed portion of the wettability changing layer, are applied by an inkjet method, and dried at 80 ° C. for 30 minutes in the air. , The light emitting layers of three colors were formed in a pattern shape.

(evaluation)

The ITO electrode and the Al electrode were provided with terminals, which were connected to a voltage source. When a voltage exceeding 6 V was applied, light emission with a peak at 620 nm in the red light emitting layer, 520 nm in the green light emitting layer, and 490 nm in the blue light emitting layer was obtained. This showed the same light emission as the photoluminescence spectrum of CdSe / ZnS quantum dots of each color protected by TOPO. In addition, in the obtained EL element, good stability, efficiency, and brightness were obtained, and good patterning titration was confirmed.

1 (a)-(c) are process charts showing an example of a method of manufacturing the EL device of the present invention.

2 is a schematic diagram illustrating quantum dots in which a ligand is disposed around.

3 is a schematic cross-sectional view showing an example of the EL element of the present invention.

4 is a schematic view for explaining phase separation of the hole transport layer and the light emitting layer in the EL device of the present invention.

5 (a)-(e) are process charts showing another example of the method of manufacturing the EL device of the present invention.

6 (a)-(b) are schematic cross-sectional views showing an example of a photocatalyst treatment layer substrate used in the present invention.

7 is a schematic cross-sectional view showing another example of the photocatalyst treatment layer substrate used in the present invention.

8 is a schematic cross-sectional view showing another example of the photocatalyst treatment layer substrate used in the present invention.

Claims (15)

A wettability changing layer forming step of forming a wettability changing layer on the substrate on which the first electrode layer is formed, containing a photocatalyst and changing wettability by the action of the photocatalyst according to energy irradiation; A wettability change pattern forming step of forming a wettability change pattern including a lyophilic region and a liquid repellent region on the surface of the wettability change layer by irradiating the wettability change layer with a pattern shape; A light emitting layer forming step of forming a light emitting layer on the lyophilic region by applying a coating solution for forming a light emitting layer containing quantum dots with ligands disposed around the wettability changing layer having a wettability changing pattern formed thereon. The manufacturing method of the electroluminescent element characterized by having. A wettability changing layer forming step of forming a wettability changing layer in which wettability is changed by the action of a photocatalyst according to energy irradiation, on a substrate having a first electrode layer formed thereon; After arranging the photocatalyst treatment layer gas on which the photocatalyst treatment layer containing at least the photocatalyst is formed on the substrate with a gap in which the action of the photocatalyst due to energy irradiation can be applied to the wettability varying layer, A wettability change pattern forming step of forming a wettability change pattern including a lyophilic region and a liquid repellent region on the surface of the wettability changing layer by irradiating with energy; A light emitting layer forming step of forming a light emitting layer on the lyophilic region by applying a coating solution for forming a light emitting layer containing quantum dots with ligands disposed around the wettability changing layer having a wettability changing pattern formed thereon. The manufacturing method of the electroluminescent element characterized by having. The manufacturing method of the electroluminescent element of Claim 1 or 2 whose said ligand is a silane coupling agent. The silane coupling agent of claim 3, wherein the silane coupling agent is YnSiX (4-n), wherein Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, and X represents an alkoxyl group, an acetyl group or a halogen and n is an integer of 0 to 3). 4. The method of claim 3, wherein the silane coupling agent is YnSiX (4-n), wherein Y represents electron transportability bonded through a functional group, direct, vinyl group or phenyl group, indicating hole transportability directly bonded through a vinyl group or a phenyl group. Silicon represented by a functional group or a functional group capable of exhibiting both hole transportability and electron transportability bonded directly through a vinyl group or a phenyl group, X represents an alkoxyl group, an acetyl group or a halogen, and n is an integer of 0 to 3). It is a compound, The manufacturing method of the electroluminescent element characterized by the above-mentioned. The manufacturing method of the electroluminescent element of Claim 3 which hardens | cures after apply | coating the said coating liquid for forming a light emitting layer in the said light emitting layer formation process. The method for manufacturing an electroluminescent element according to claim 1 or 2, wherein the coating liquid for forming the light emitting layer further contains at least one or more of a hole transport material and an electron transport material. The electroluminescence according to claim 1 or 2, wherein the quantum dot has a core portion containing semiconductor fine particles, and a shell portion covering the core portion and containing a material having a larger band gap than the semiconductor fine particles. Method of manufacturing the device. The manufacturing method of the electroluminescent element of Claim 1 or 2 in which the coating method of the coating liquid for light emitting layer formation includes a discharge method. The wettability changing layer according to claim 1 or 2, wherein the wettability changing layer is YnSiX (4-n), wherein Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, and X represents an alkoxyl group, an acetyl group. Or halogen, and n is an integer of 0 to 3). The production of an electroluminescent device comprising organopolysiloxane which is one or two or more hydrolysis condensates or cohydrolysis condensates. Way. Substrate, A first electrode layer formed in a pattern on the substrate; It is formed on the first electrode layer, the wettability is changed by the action of the photocatalyst according to the energy irradiation, disposed on the pattern of the first electrode layer, the lyophilic region containing polysiloxane and the opening of the pattern of the first electrode layer A wettability change layer having a wettability change pattern comprising a liquid-repellent region containing an organopolysiloxane containing fluorine corresponding thereto; A light emitting layer formed on the lyophilic region of the wettability changing layer, It has a second electrode layer formed on the light emitting layer, The luminescent element uses the quantum dot arrange | positioned around the said light emitting layer, The electroluminescent element characterized by the above-mentioned. The electroluminescent device according to claim 11, wherein the light emitting layer contains a hydrolysis condensate of the silane coupling agent and is cured. 13. The hydrolysis condensation product of claim 12, wherein the hydrolysis condensate of the silane coupling agent is YnSiX (4-n), wherein Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, and X represents an alkoxyl group, acetyl And an organopolysiloxane which is one or two or more hydrolysis condensates or co-hydrolysis condensates among the silicon compounds represented by the group or halogen and n is an integer of 0 to 3). The method according to claim 12, wherein the hydrolysis condensate of the silane coupling agent is YnSiX (4-n), wherein Y is directly through a functional group, a direct group, a vinyl group or a phenyl group which exhibits hole transporting properties through a vinyl group or a phenyl group. A functional group which shows the bonded electron transport property, or the functional group which can represent both the hole transport property and the electron transport property which were couple | bonded directly through the vinyl group or the phenyl group, X represents an alkoxyl group, an acetyl group, or a halogen, n is an integer of 0-3 An organopolysiloxane which is one or two or more hydrolysis condensates or cohydrolysis condensates of the silicon compound represented by the above. The electroluminescent device according to claim 11, wherein the quantum dot has a core portion containing semiconductor fine particles, and a shell portion covering the core portion and containing a material having a larger band gap than the semiconductor fine particles.

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